Use of strobilurin type compounds for combating phytopathogenic fungi resistant to Qo inhibitors

ABSTRACT

The present invention relates to the use of strobilurine type compounds of formula I and the N-oxides and the salts thereof for combating phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, and to methods for combating such fungi. The invention also relates to novel compounds, processes for preparing these compounds, to compositions comprising at least one such compound, to plant health applications, and to seeds coated with at least one such compound.

This application is a continuation of U.S. application Ser. No.14/364,532, filed Jun. 11, 2014, the entire contents of which is herebyincorporated herein by reference. U.S. application Ser. No. 14/364,532,is the National Stage application of International Application No.PCT/EP2012/074586, filed Dec. 6, 2012, the entire contents of which ishereby incorporated herein by reference. U.S. application Ser. No.14/364,532, also claims priority under 35 U.S.C. § 119 to EuropeanPatent Application No. 11195032.5, filed Dec. 21, 2011, and to EuropeanPatent Application No. 12190109.4, filed Oct. 26, 2012, the entirecontents of both of which are hereby incorporated herein by reference.

The present invention relates to the use of strobilurine type compoundsof formula I and the N-oxides and the salts thereof for combatingphytopathogenic fungi containing a mutation in the mitochondrialcytochrome b gene conferring resistance to Qo inhibitors, and to methodsfor combating such fungi. The invention also relates to novel compounds,processes for preparing these compounds, to compositions comprising atleast one such compound, to plant health applications, and to seedscoated with at least one such compound.

Qo inhibitor fungicides, often referred to as strobilurin-typefungicides (Sauter 2007: Chapter 13.2. Strobilurins and other complexIII inhibitors. In: Kramer, W.; Schirmer, U. (Ed.)—Modern CropProtection Compounds. Volume 2. Wiley-VCH Verlag 457-495), areconventionally used to control a number of fungal pathogens in crops. Qoinhibitors typically work by inhibiting respiration by binding to aubihydroquinone oxidation center of a cytochrome bc₁ complex (electrontransport complex III) in mitochondria. Said oxidation center is locatedon the outer side of the inner mitochrondrial membrane. A prime exampleof the use of Qo inhibitors includes the use of, for example,strobilurins on wheat for the control of Septoria tritici (also known asMycosphaerella graminicola), which is the cause of wheat leaf blotch.Unfortunately, widespread use of such Qo inhibitors has resulted in theselection of mutant pathogens which are resistant to such Qo inhibitors(Gisi et al., Pest Manag Sci 56, 833-841, (2000). Resistance to Qoinhibitors has been detected in several phytopathogenic fungi such asBlumeria graminis, Mycosphaerella fijiensis, Pseudoperonspora cubensisor Venturia inaequalis. Although several resistance mechanisms have beendetected meanwhile (e.g. Jabs et al. Phytomedizin 31, 15-16 (2001);Olaya et al., Pestic Sci 54, 230-236 (1998), the major part ofresistance to Qo inhibitors in agricultural uses has been attributed topathogens containing a single amino acid residue substitution G143A inthe cytochrome b gene for their cytochrome bc₁ complex, the targetprotein of Qo inhibitors. See, for example, Lucas, Pestic Outlook 14(6),268-70 (2003); and Fraaije et al., Phytopathol 95(8), 933-41 (2005),(which both are expressly incorporated by reference herein). Thus, newmethods and compositions are desirable for controlling pathogen induceddiseases in crops comprising plants subjected to pathogens that areresistant to Qo inhibitors. Furthermore, in many cases, in particular atlow application rates, the fungicidal activity of the known fungicidalstrobilurin analogue compounds is unsatisfactory, especially in casethat a high proportion of the fungal pathogens contain a mutation in themitochondrial cytochrome b gene conferring resistance to Qo inhibitors.Based on this, it was also an object of the present invention to providecompounds having improved activity and/or a broader activity spectrumagainst phytopathogenic harmful fungi.

“Qo inhibitor,” as used herein, includes any substance that is capableof diminishing and/or inhibiting respiration by binding to aubihydroquinone oxidation center of a cytochrome bc₁ complex inmitochondria. The oxidation center is typically located on the outerside of the inner mitochrondrial membrane.

From WO 2009/155095, the use of a Qi inhibitor UK2A of formula

is known for combating phytopathogenic fungi that are resistant to Qoinhibitors. Qi inhibitors typically work by inhibiting respiration bybinding to a ubihydroquinone oxidation center of a cytochrome bclcomplex in mitochondria, the said oxidation center being located on theinner side of the inner mitochrondrial membrane.

The strobilurin-analogue compounds according to the present inventiondiffer from those described in the abovemention publication by thespecific formula I and by inhibiting respiration by binding to aubihydroquinone oxidation center of a cytochrome bcl complex inmitochondria which defines them as Qo inhibitors. Besides thestrobilurin analogue-specific structural elements R⁴, these compoundscontain two specific carbon atoms bound by a double bond wherein thegroups R¹ and R² are cis-oriented or the R¹ and R² together with theabovementioned two carbon atoms linking them form a phenyl ring if R⁴ is4-methyl-1,4-dihydro-tetrazol-5-on-1-yl.

BRIEF DESCRIPTION OF THE INVENTION

-   -   Accordingly, the present invention relates to the use of        compounds of formula I

wherein:

-   R¹,R² independently of each other are hydrogen, halogen,    C₁-C₄-alkyl, C₁-C₄-alkoxy, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy,    C₂-C₆-alkynyl, C₃-C₆-cycloalkyl or C₃-C₆-cycloalkyl-C₁-C₄-alkyl,    wherein the groups R¹ and R² are cis-oriented, or    -   R¹ and R² together with the two carbon atoms linking them form a        phenyl ring provided that R⁴ is        4-methyl-1,4-dihydro-tetrazol-5-one-1-yl (formula R4-7), and        -   wherein the aliphatic moieties of R′ and/or R² or the            abovementioned phenyl ring may carry 1, 2, 3 or up to the            maximum number of identical or different groups IV which            independently of one another are selected from:    -   R^(a) halogen, CN, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy,        C₁-C₄-haloalkyl and C₁-C₄-haloalkoxy;-   Y is a direct bond or a divalent group selected from —OCH₂—, —CH₂—,    —CH₂CH₂—, —C(Z)═NO—CH₂—, —CHZ—C(Z)═NO—CH₂—, —O—N═C(Z)—C(Z)═NO—CH₂—,    —C(═O)—C(Z)═NO—CH₂— and —C(═N—O—Z)—C(Z)═NO—CH₂—,    -   where the bond depicted on the left side of the divalent group Y        is attached to R³, and the bond depicted on the right side is        attached to the carbon atom being substituted by R², and    -   Z, which may be the same or different to any other Z, is        hydrogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl;-   R³ is phenyl or a 3- to 10-membered saturated, partially unsaturated    or aromatic mono- or bicyclic heterocyclyl wherein the ring member    atoms of the heterocyclyl include besides carbon atoms 1, 2, 3 or 4    heteroatoms selected from the group of N, O and S;    -   wherein the cyclic groups R³ may carry 1, 2, 3, 4 or up to the        maximum possible number of identical or different groups R³        which independently of one another are selected from:    -   R^(b), which may be the same or different to any other R^(b), is        amino, halogen, hydroxyl, oxo, nitro, CN, carboxyl, C₁-C₄-alkyl,        C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,        C₁-C₄-haloalkoxy, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkenyl,        C₂-C₆-alkenyloxy, C₃-C₆-alkynyloxy,        C₂-C₆-alkenyloxyimino-C₁-C₄-alkyl,        C₂-C₆-alkynyloxyimino-C₁-C₄-alkyl, C₁-C₄-alkylamino,        C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylcarbonyloxy, phenyl, naphthyl        or a 3- to 10-membered saturated, partially unsaturated or        aromatic mono- or bicyclic heterocyclyl which, in addition to        carbon atoms, contains one to four heteroatoms from the group        consisting of N, O and S as ring members; and wherein the        aforementioned phenyl and heterocyclyl groups R^(b) are attached        via a direct bond, an oxygen or sulfur atom, and        -   two radicals R^(b) that are bound to adjacent ring member            atoms of the cyclic group R³ may form together with said            ring member atoms a fused 5-, 6- or 7-membered saturated,            partially unsaturated or aromatic cycle, which may be a            carbocycle or heterocycle, wherein the ring member atoms of            the heterocycle include besides carbon atoms 1, 2, 3 or 4            heteroatoms selected from the group of N, O and S,        -   and        -   where the aliphatic or cyclic groups R^(b) for their part            may carry 1, 2, 3 or up to the maximum possible number of            identical or different groups R^(c):        -   R^(c), which may be the same or different to any other            R^(c), is halogen, hydroxyl, nitro, CN, carboxyl,            C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₈-alkynyl, C₁-C₄-haloalkyl,            C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,            C₁-C₆-alkoxyimino-C₁-C₄-alkyl,            C₂-C₆-alkenyloxyimino-C₁-C₄-alkyl,            C₂-C₆-alkynyloxyimino-C₁-C₄-alkyl, C₁-C₆-alkoxyimino-,            C₂-C₆-alkenyloxyimino-, C₂-C₆-alkynyloxyimino-,            C₂-C₆-haloalkenyloxyimino-, C₃-C₆-cycloalkyl,            C₃-C₆-cycloalkenyl, phenyl or a 5-membered saturated,            partially unsaturated or aromatic heterocyclyl which, in            addition to carbon atoms, contains one to three heteroatoms            from the group consisting of N, O and S as ring members;            wherein the aforementioned cyclic groups R^(c) are attached            via a direct bond, an oxygen or sulfur atom, and where the            aliphatic or cyclic groups R^(c) for their part may carry 1,            2, 3 or up to the maximum possible number of identical or            different groups R^(d):        -   R^(d), which may be the same or different to any other            R^(d), is halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl;    -   or-   R³ is —CR^(A)═N—O—R^(B), wherein    -   R^(A) is amino, hydroxyl, C₁-C₄-alkyl, C₂-C₄-alkenyl,        C₂-C₄-alkynyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,        C₃-C₆-cycloalkyl, C₃-C₆-cycloalkenyl, C₂-C₆-alkenyloxy,        C₃-C₆-alkynyloxy, C₁-C₄-alkoxyimino-C₁-C₄-alkyl,        C₁-C₄-alkylamino, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylcarbonyloxy,        phenyl, phenyl-C₁-C₄-alkyl, naphthyl or a 3- to 10-membered        saturated, partially unsaturated or aromatic mono- or bicyclic        heterocyclyl which, in addition to carbon atoms, contains one to        four heteroatoms from the group consisting of O, N and S as ring        members; and wherein the aforementioned cyclic R^(A) are        attached via a direct bond, an oxygen or sulfur atom;    -   R^(B) is C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl,        C₁-C₄-haloalkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkenyl,        C₁-C₄-alkoxyimino-C₁-C₄-alkyl, C₁-C₄-alkoxycarbonyl, phenyl,        phenyl-C₁-C₄-alkyl, naphthyl or a 3- to 10-membered saturated,        partially unsaturated or aromatic mono- or bicyclic heterocyclyl        which, in addition to carbon atoms, contains one to four        heteroatoms from the group consisting of O, N and S as ring        members;    -   where the aliphatic or cyclic groups R^(A) and/or R^(B) for        their part may carry 1, 2, 3 or up to the maximum possible        number of identical or different groups R^(e):    -   R^(e), which may be the same or different to any other R^(e), is        halogen, hydroxyl, nitro, CN, carboxyl, C₁-C₄-alkyl,        C₂-C₄-alkenyl, C₂-C₈-alkynyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or        C₁-C₄-haloalkoxy;-   R⁴ is a monovalent group selected from formulae R4-1 to R4-7

-   -   wherein the jagged line defines the point of attachment, and    -   X is a direct bond or a divalent group CH₂, 0 or NH,    -   R⁵ is C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl,        C₁-C₄-haloalkoxy or C₃-C₆-cycloalkyl,    -   R⁶ is C₁-C₄-alkyl or C₁-C₄-haloalkyl;        and the N-oxides and the agriculturally acceptable salts        thereof, for combating phytopathogenic fungi containing a        mutation in the mitochondrial cytochrome b gene conferring        resistance to Qo inhibitors.

Furthermore, the present invention also relates to methods for combatingphytopathogenic fungi containing a mutation in the mitochondrialcytochrome b gene conferring resistance to Qo inhibitors using theabovementioned compounds of formula I.

Certain strobilurin type compounds of formula I, wherein R⁴ is1-methoxycarbonyl-2-methoxy-ethen-1-yl (defined as R4-2 herein, whereinX is O) and R¹ is CF₃, are mentioned in WO 1998/021174:(E)-2-[1-methoxy-meth-(E)-ylidene]-5-(4-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoicacid methyl ester (CAS No. 207852-99-1);(E)-2-[1-methoxy-meth-(E)-ylidene]-5-(3-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoicacid methyl ester (207853-00-7);(E)-2-[1-methoxy-meth-(E)-ylidene]-4-methyl-5-(3-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoicacid methyl ester; and(E)-5,5,5-trifluoro-2-[1-methoxy-meth-(E)-ylidene]-3-methyl-4-(4-phenoxy-phenoxymethyl)-pent-3-enoicacid methyl ester. However, it is not mentioned that the strobilurinetype compounds inhibit fungal pathogens containing a mutation in themitochondrial cytochrome b gene conferring resistance to Qo inhibitors.II

Further, preparation of the compound(2E,3Z)-2-(ethylidene)-5-phenyl-3-pentenoic acid methyl ester (CAS-No.681026-20-0) has been described in J Organomet Chem 689, 575-584 (2004).

Further, certain strobilurin type compounds, wherein R¹ and R² togetherwith the two carbon atoms linking them form a phenyl ring and wherein R⁴is 1-methyl-1,4-dihydro-tetrazole-5-one-4-yl (R4-7) are known inter aliafrom WO 1996/036229, WO 1999/046246 and DE 199 00 571 A1.

The compounds according to the present invention differ from thosedescribed in the abovementioned publications that R¹ and R² do not formwith the two carbon atoms linking them a phenyl ring, and that(E)-2-[1-methoxy-meth-(E)-ylidene]-5-(4-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoicacid methyl ester (207852-99-1);(E)-2-[1-methoxy-meth-(E)-ylidene]-5-(3-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoicacid methyl ester (207853-00-7);(E)-2-[1-methoxy-meth-(E)-ylidene]-4-methyl-5-(3-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoicacid methyl ester;(E)-5,5,5-trifluoro-2-[1-methoxy-meth(E)-ylidene]-3-methyl-4-(4-phenoxy-phenoxymethyl)-pent-3-enoicacid methyl ester; and (2E,3Z)-2-(ethylidene)-5-phenyl-3-pentenoic acidmethyl ester (CAS-No. 681026-20-0) are excluded.

Therefore, according to a second aspect, the invention providescompounds of formula I which are represented by formula I

wherein:

-   R¹,R² independently of each other are hydrogen, halogen,    C₁-C₄-alkyl, C₁-C₄-alkoxy, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy,    C₂-C₆-alkynyl, C₃-C₆-cycloalkyl or C₃-C₆-cycloalkyl-C₁-C₄-alkyl,    wherein the groups R¹ and R² are cis-oriented,    -   wherein the aliphatic moieties of R¹ and/or R² may carry 1, 2, 3        or up to the maximum number of identical or different groups IV        which independently of one another are selected from:    -   R^(a) halogen, CN, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy,        C₁-C₄-haloalkyl and C₁-C₄-haloalkoxy;-   Y is a direct bond or a divalent group selected from —OCH₂—, —CH₂—,    —CH₂CH₂—, —C(Z)═NO—CH₂—, —CHZ—C(Z)═NO—CH₂—, —O—N═C(Z)—C(Z)═NO—CH₂—,    —C(═O)—C(Z)═NO—CH₂— and —C(═N—O—Z)—C(Z)═NO—CH₂—,    -   where the bond depicted on the left side of the divalent group Y        is attached to R³, and the bond depicted on the right side is        attached to the carbon atom being substituted by R², and    -   Z, which may be the same or different to any other Z, is        C₁-C₄-alkyl or C₁-C₄-haloalkyl;-   R³ is phenyl or a 3- to 10-membered saturated, partially unsaturated    or aromatic mono- or bicyclic heterocyclyl wherein the ring member    atoms of the heterocyclyl include besides carbon atoms 1, 2, 3 or 4    heteroatoms selected from the group of N, O and S;    -   wherein the cyclic groups R³ may carry 1, 2, 3, 4 or up to the        maximum possible number of identical or different groups R^(b)        which independently of one another are selected from:    -   R^(b), which may be the same or different to any other R^(b), is        amino, halogen, hydroxyl, oxo, nitro, CN, carboxyl, C₁-C₄-alkyl,        C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,        C₁-C₄-haloalkoxy, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkenyl,        C₂-C₆-alkenyloxy, C₃-C₆-alkynyloxy,        C₁-C₆-alkoxyimino-C₁-C₄-alkyl,        C₂-C₆-alkenyloxyimino-C₁-C₄-alkyl,        C₂-C₆-alkynyloxyimino-C₁-C₄-alkyl, C₁-C₄-alkylamino,        C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylcarbonyloxy, phenyl, naphthyl        or a 3- to 10-membered saturated, partially unsaturated or        aromatic mono- or bicyclic heterocyclyl which, in addition to        carbon atoms, contains one to four heteroatoms from the group        consisting of N, O and S as ring members; and wherein the        aforementioned phenyl and heterocyclyl groups R^(b) are attached        via a direct bond, an oxygen or sulfur atom;        -   and        -   two radicals R^(b) that are bound to adjacent ring member            atoms of the cyclic group R³ may form together with said            ring member atoms a fused 5-, 6- or 7-membered saturated,            partially unsaturated or aromatic cycle, which may be a            carbocycle or heterocycle,        -   wherein the ring member atoms of the fused heterocycle            include besides carbon atoms 1, 2, 3 or 4 heteroatoms            selected from the group of N, O and S, and        -   where the aliphatic or cyclic groups R^(b) for their part            may carry 1, 2, 3 or up to the maximum possible number of            identical or different groups R^(c):        -   R^(c), which may be the same or different to any other            R^(c), is halogen, hydroxyl, nitro, CN, carboxyl,            C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₈-alkynyl, C₁-C₄-haloalkyl,            C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,            C₁-C₆-alkoxyimino-C₁-C₄-alkyl,            C₂-C₆-alkenyloxyimino-C₁-C₄-alkyl,            C₂-C₆-alkynyloxyimino-C₁-C₄-alkyl,            C₁-C₄-alkoxyimino-C₁-C₄-alkyl, C₁-C₆-alkoxyimino-,            C₂-C₆-alkenyloxyimino-, C₂-C₆-alkynyloxyimino-,            C₂-C₆-haloalkenyloxyimino-, C₃-C₆-cycloalkyl,            C₃-C₆-cycloalkenyl, phenyl or a 5-membered saturated,            partially unsaturated or aromatic heterocyclyl which, in            addition to carbon atoms, contains one to three heteroatoms            from the group consisting of N, O and S as ring members;            wherein the aforementioned cyclic groups R^(c) are attached            via a direct bond, an oxygen or sulfur atom and where the            aliphatic or cyclic groups R^(c) for their part may carry 1,            2, 3 or up to the maximum possible number of identical or            different groups R^(d):        -   R^(d), which may be the same or different to any other            R^(d), is halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl;    -   or-   R³ is —CR^(A)═N—O—R^(B), wherein    -   R^(A) is amino, hydroxyl, C₁-C₄-alkyl, C₂-C₄-alkenyl,        C₂-C₄-alkynyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,        C₃-C₆-cycloalkyl, C₃-C₆-cycloalkenyl, C₂-C₆-alkenyloxy,        C₃-C₆-alkynyloxy, C₁-C₄-alkoxyimino-C₁-C₄-alkyl,        C₁-C₄-alkylamino, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylcarbonyloxy,        phenyl, phenyl-C₁-C₄-alkyl, naphthyl or a 3- to 10-membered        saturated, partially unsaturated or aromatic mono- or bicyclic        heterocyclyl which, in addition to carbon atoms, contains one to        four heteroatoms from the group consisting of O, N and S as ring        members; and wherein the aforementioned cyclic R^(A) are        attached via a direct bond, an oxygen or sulfur atom;    -   R^(B) is C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl,        C₁-C₄-haloalkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkenyl,        CC₁-C₄-alkoxyimino-C₁-C₄-alkyl, C₁-C₄-alkoxycarbonyl, phenyl,        phenyl-C₁-C₄-alkyl, naphthyl or a 3- to 10-membered saturated,        partially unsaturated or aromatic mono- or bicyclic heterocyclyl        which, in addition to carbon atoms, contains one to four        heteroatoms from the group consisting of O, N and S as ring        members;        -   where the aliphatic or cyclic groups R^(A) and/or R^(B) for            their part may carry 1, 2, 3 or up to the maximum possible            number of identical or different groups R^(e):        -   R^(e), which may be the same or different to any other            R^(e), is halogen, hydroxyl, nitro, CN, carboxyl,            C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₈-alkynyl, C₁-C₄-haloalkyl,            C₁-C₄-alkoxy or C₁-C₄-haloalkoxy;-   R⁴ is a monovalent group selected from formulae R4-1 to R4-7

-   -   wherein the jagged line defines the point of attachment, and        where    -   X is a divalent group 0 or NH,    -   R⁵ is C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl,        C₁-C₄-haloalkoxy or C₃-C₆-cycloalkyl,    -   R⁶ is C₁-C₄-alkyl or C₁-C₄-haloalkyl;

-   and the N-oxides and the agriculturally acceptable salts thereof,    except for    (E)-2-[1-methoxy-meth-(E)-ylidene]-5-(4-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoic    acid methyl ester (207852-99-1),    (E)-2-[1-methoxy-meth-(E)-ylidene]-5-(3-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoic    acid methyl ester (207853-00-7);    (E)-2-[1-methoxy-meth-(E)-ylidene]-4-methyl-5-(3-phenoxy-phenoxy)-3-trifluoromethyl-pent-3-enoic    acid methyl ester,    (E)-5,5,5-trifluoro-2-[1-methoxy-meth-(E)-ylidene]-3-methyl-4-(4-phenoxy-phenoxymethyl)-pent-3-enoic    acid methyl ester, and (2E,3Z)-2-(ethylidene)-5-phenyl-3-pentenoic    acid methyl ester (CAS-No. 681026-20-0).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1: The commercially available strobilurin analogue compoundPyraclostrobin modelled into an artificial cytochrome bc₁ complexQo-binding site displays steric clash of the phenyl ring with the 143Amethyl group as indicated by arrow in the upper right part of thepicture (see left picture). Compound 1-6 according to the presentinvention does not show a steric clash (see right picture).

DETAILED DESCRIPTION OF THE INVENTION

The term “compounds I” refers to compounds of formula I. Likewise, thisterminology applies to all sub-formulae, e. g. “compounds I.2” refers tocompounds of formula I.2 or “compounds V” refers to compounds of formulaV, etc.

The compounds I can be obtained by various routes in analogy to priorart processes known (e.g. WO 1998/021174, J Organomet Chem 689, 575-584(2004), WO 1996/036229) and, advantageously, by the synthesis shown inthe following schemes and in the experimental part of this application.

A suitable method to prepare compounds I is illustrated in scheme 1. Itstarts with the reduction of an acetylene compound II with a reducingagent like lithium aluminium hydride preferably in the presence of asolvent. Suitable solvents are inert against the reducing agent used andpreferably selected from cyclic or aliphatic ethers like dietyl ether,tetrahydrofurane (THF), 1,4-dioxane, and methyl-tert.-butyl ether(MTBE). The reaction temperature can be between −40° C. and 100° C.,preferably −20 to 60° C. After a reduced intermediate has been formed, atin compound of formula III, wherein Alk defines a suitable alkylresidue like methyl, ethyl, n-propyl, or n-butyl and wherein L is aleaving group such as halogen, ethoxy and methoxy, in particularmethoxy, is added. The resulting intermediate IV is a stable compoundwhich can be isolated and purified with the usual methods (for exampleextraction and chromatography).

Compound IV is further reacted with compound V to yield the intermediateVI applying the usual methods for coupling aliphatic alcohols withhydroxyl compounds IV. The Mitsonobu reaction has proven especiallyuseful.

Compound VI is then coupled with compound VII, wherein LG is a leavinggroup, preferably being halogen (except fluoro) or a sulfonyloxy groupsuch as triflate, preferably in the presence of a suitable catalyst suchas known transition metal catalysts, more preferably palladiumcatalalysts, wherein the ligand may ber trifuryl phoshine, triphenylphosphine, tritolyl phosphine or bidentate phosphine ligands. The.Copper compounds, such as CuI₂ can be added to improve the reaction. Awide variety of solvents is possible here, with THF, 1,4-dioxane andamides like dimethylformamide (DMF) being preferred. The reactiontemperatures can be −20 to 150° C., preferably 20 to 120° C.

The resulting compounds I, wherein Y is —OCH₂— and R² is H, can befurther modified. For example, if R⁴ contains an ester group, VIII canbe transformed into a methyl amide by reaction ith methyl amine.

Another general method to prepare compounds I is illustrated in scheme2. The starting materials VIII are either known or can be preparedanalogous to known compounds. The Wittig-Horner reaction of compoundsVIII with compounds IX illustrated here (see also Tetrahedron Lett.1988, 29, 3361) can be replaced by the Wittig reaction if this resultsin better yields. These reactions as well as the reaction conditions arewell known. A specific problem is the E/Z-ratio in the newly formeddouble bond. The desired isomer is usually accompanied by some undesiredisomer, which has to be removed by purification known in the art (e. g.chromatography, destillation, crystallization, etc.).

A route to compounds I, wherein R⁴ is of formula R4-4, is illustrated inscheme 3. The compound X can be obtained for example from compound VI bydirect reaction with iodine. The iodine in compounds X may be replacedby other suitable leaving groups, for example by bromine, chlorine ortriflate. The sodium atom in the salt VII can be replaced by othersuitable metal atoms, for example potassium, lithium, magnesium,calcium, etc. The coupling reaction of X and XI is performed preferablyin the presence of a transition metal catalyst being preferably copperin the presence of a nitrogen containing ligand system (see e.g.:Tetrahedron Lett 2008, 49 (26), 4196-4199; Org Lett. 2004, 6 (11),1809-1812).

If individual compounds I cannot be obtained by the routes describedabove, they can be prepared by derivatization of other compounds I.

If the synthesis yields mixtures of isomers in the case of oximes, aseparation is generally not necessarily required since in some cases theindividual isomers can be interconverted during work-up for use orduring application (e. g. under the action of light, acids or bases).Such conversions may also take place after use, e. g. in the treatmentof plants in the treated plant, or in the harmful fungus to becontrolled.

In the definitions of the variables given above, collective terms areused which are generally representative for the substituents inquestion. The term “C_(n)-C_(m)” indicates the number of carbon atomspossible in each case in the substituent or substituent moiety inquestion.

The term “halogen” refers to fluorine, chlorine, bromine and iodine.

The term “C₁-C₆-alkyl” refers to a straight-chained or branchedsaturated hydrocarbon group having 1 to 6 carbon atoms, e.g. methyl,ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl(isobutyl), 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl,1,2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl,3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and1-ethyl-2-methylpropyl. Likewise, the term “C₁-C₄-alkyl” refers to astraight-chained or branched alkyl group having 1 to 4 carbon atoms.

The term “C₁-C₄-haloalkyl” refers to a straight-chained or branchedalkyl group having 1 to 4 carbon atoms (as defined above), wherein someor all of the hydrogen atoms in these groups may be replaced by halogenatoms as mentioned above, for example chloromethyl, bromomethyl,dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl,trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl,chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl,2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl,2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl,2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl,2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl,3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, CH₂—C₂F₅,CF₂—C₂F₅, CF(CF₃)₂, 1-(fluoromethyl)-2-fluoroethyl,1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl,4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl. Likewise,the term “C₁-C₆-haloalkyl” refers to a straight-chained or branchedalkyl group having 1 to 6 carbon atoms.

The term “C₁-C₆-alkoxy” refers to a straight-chain or branched alkylgroup having 1 to 6 carbon atoms which is bonded via an oxygen, at anyposition in the alkyl group, e.g. OCH₃, OCH₂CH₃, O(CH₂)₂CH₃,1-methylethoxy, O(CH₂)₃CH₃, 1-methylhpropoxy, 2-methylpropoxy or1,1-dimethylethoxy, O(CH₂)₄CH₃ or O(CH₂)₅CH₃. Likewise, the term“C₁-C₄-alkoxy” refers to a straight-chain or branched alkyl group having1 to 4 carbon atoms which is bonded via an oxygen, at any position inthe alkyl group.

The term “C₁-C₄-haloalkoxy” refers to a C₁-C₄-alkoxy group as definedabove, wherein some or all of the hydrogen atoms may be replaced byhalogen atoms as mentioned above, for example, OCH₂F, OCHF₂, OCF₃,OCH₂Cl, OCHCl₂, OCCl₃, chlorofluoromethoxy, dichlorofluoromethoxy,chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy,2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy,2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy,2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloro-ethoxy, OC₂F₅,2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy,2,3-difluoro-propoxy, 2-chloropropoxy, 3-chloropropoxy,2,3-dichloropropoxy, 2-bromo-propoxy, 3-bromopropoxy,3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH₂—C₂F₅, OCF₂—C₂F₅,1-(CH₂F)-2-fluoroethoxy, 1-(CH₂Cl)-2-chloroethoxy,1-(CH₂Br)-2-bromo-ethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxyor nonafluorobutoxy. Likewise, the term “C₁-C₆-haloalkoxy” refers to aC₁-C₆-alkoxy group as defined above, wherein some or all of the hydrogenatoms may be replaced by halogen atoms as mentioned above.

The term “C₁-C₄-alkoxy-C₁-C₄-alkyl” refers to alkyl having 1 to 4 carbonatoms, wherein one hydrogen atom of the alkyl radical is replaced by aC₁-C₄-alkoxy group. Likewise, the term “C₁-C₆-alkoxy-C₁-C₆-alkyl” refersto alkyl having 1 to 6 carbon atoms, wherein one hydrogen atom of thealkyl radical is replaced by a C₁-C₆-alkoxy group.

The term “C₁-C₄-alkylamino” refers to an amino radical carrying oneC₁-C₄-alkyl group as substituent, e.g. methylamino, ethylamino,propylamino, 1-methylethylamino, butylamino, 1-methylpropylamino,2-methylpropylamino, 1,1-dimethylethylamino and the like. Likewise, theterm “C₁-C₆-alkylamino” refers to an amino radical carrying oneC₁-C₆-alkyl group as substituent.

The term “di(C₁-C₄-alkyl)amino” refers to an amino radical carrying twoidentical or different C₁-C₄-alkyl groups as substituents, e. g.dimethylamino, diethylamino, di-n-propylamino, diisopropylamino,N-ethyl-N-methylamino, N-(n-propyl)-N-methylamino, N-(isopropyl)-Nmethylamino, N-(n-butyl)-N-methylamino, N-(2-butyl)-N methylamino,N-(isobutyl)-N-methylamino, and the like. Likewise, the term“di(C₁-C₆-alkyl)amino” refers to an amino radical carrying two identicalor different C₁-C₆-alkyl groups as substituents.

The term “C₁-C₄-alkoxyimino” refers to a divalent imino radical(C₁-C₄-alkyl-O—N═) carrying one C₁-C₄-alkoxy group as substituent, e.g.methylimino, ethylimino, propylimino, 1-methylethylimino, butylimino,1-methylpropylimino, 2-methylpropylimino, 1,1-dimethylethylimino and thelike.

The term “C₁-C₆-alkoxyimino-C₁-C₄-alkyl” refers to alkyl having 1 to 4carbon atoms (as defined above), wherein two hydrogen atoms of onecarbon atom of the alkyl radical are replaced by a divalentC₁-C₆-alkoxyimino radical (C₁-C₆-alkyl-O—N═) as defined above.

The term “C₂-C₆-alkenyloxyimino-C₁-C₄-alkyl” refers to alkyl having 1 to4 carbon atoms (as defined above), wherein two hydrogen atoms of onecarbon atom of the alkyl radical are replaced by a divalentC₂-C₆-alkenyloxyimino radical (C₂-C₆-alkenyl-O—N═).

The term “C₂-C₆-alkynyloxyimino-C₁-C₄-alkyl” refers to alkyl having 1 to4 carbon atoms (as defined above), wherein two hydrogen atoms of onecarbon atom of the alkyl radical are replaced by a divalentC₂-C₆-alkynyloxyimino radical (C₂-C₆-alkynyl-O—N═).

The term “C₁-C₄-alkylcarbonyl” refers to a C₁-C₄-alkyl radical which isattached via a carbonyl group. The term “(C₁-C₆-alkoxy)carbonyl” refersto a C₁-C₆-alkoxy radical which is attached via a carbonyl group.

The term “C₁-C₆-alkylaminocarbonyl” refers to a C₁-C₆-alkylamino radicalwhich is attached via a carbonyl group. Likewise, the term“di(C₁-C₆-alkyl)aminocarbonyl” refers to a di(C₁-C₆)alkylamino radicalwhich is attached via a carbonyl group.

The term “C₂-C₄-alkenyl” refers to a straight-chain or branchedunsaturated hydrocarbon radical having 2 to 4 carbon atoms and a doublebond in any position, e.g. ethenyl, 1-propenyl, 2-propenyl (allyl),1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl,2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl. Likewise,the term “C₂-C₆-alkenyl” refers to a straight-chain or branchedunsaturated hydrocarbon radical having 2 to 6 carbon atoms and a doublebond in any position.

The term “C₂-C₄-alkynyl” refers to a straight-chain or branchedunsaturated hydrocarbon radical having 2 to 4 carbon atoms andcontaining at least one triple bond, such as ethynyl, 1-propynyl,2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl.Likewise, the term “C₂-C₆-alkynyl” refers to a straight-chain orbranched unsaturated hydrocarbon radical having 2 to 6 carbon atoms andat least one triple bond.

The term “C₃-C₆-cycloalkyl” refers to monocyclic, bicyclic, saturatedhydrocarbon radicals having 3 to 6 carbon ring members, such ascyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Likewise, the term “C₃-C₆-cycloalkenyl” refers to unsaturatedhydrocarbon radicals having 3 to 6 carbon ring members and a double bondin any position, such as cyclopropenyl, cyclobutenyl, cyclopentenyl orcyclohexenyl.

The term “C₃-C₆-cycloalkyl-C₁-C₄-alkyl” refers to alkyl having 1 to 4carbon atoms (as defined above), wherein one hydrogen atom of the alkylradical is replaced by a cycloalkyl radical having 3 to 6 carbon atoms.

The term “phenyl-C₁-C₄-alkyl” refers to alkyl having 1 to 4 carbon atoms(as defined above), wherein one hydrogen atom of the alkyl radical isreplaced by a phenyl radical.

Agriculturally acceptable salts of compounds I encompass especially thesalts of those cations or the acid addition salts of those acids whosecations and anions, respectively, have no adverse effect on thefungicidal action of the compounds I. Suitable cations are thus inparticular the ions of the alkali metals, preferably sodium andpotassium, of the alkaline earth metals, preferably calcium, magnesiumand barium, of the transition metals, preferably manganese, copper, zincand iron, and also the ammonium ion which, if desired, may carry one tofour C₁-C₄-alkyl substituents and/or one phenyl or benzyl substituent,preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium,trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions,preferably tri(C₁-C₄-alkyl)sulfonium, and sulfoxonium ions, preferablytri(C₁-C₄-alkyl)sulfoxonium. Anions of useful acid addition salts areprimarily chloride, bromide, fluoride, hydrogensulfate, sulfate,dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate,carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and theanions of C₁-C₄-alkanoic acids, preferably formate, acetate, propionateand butyrate. They can be formed by reacting a compound of formula Iwith an acid of the corresponding anion, preferably of hydrochloricacid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

The compounds of formula I can be present in atropisomers arising fromrestricted rotation about a single bond of asymmetric groups. They alsoform part of the subject matter of the present invention.

Depending on the substitution pattern, the compounds of formula I andtheir N-oxides may have one or more centers of chirality, in which casethey are present as pure enantiomers or pure diastereomers or asenantiomer or diastereomer mixtures. Both, the pure enantiomers ordiastereomers and their mixtures are subject matter of the presentinvention.

In respect of the variables, the embodiments of the intermediatescorrespond to the embodiments of the compounds I.

Preference is given to those compounds I and where applicable also tocompounds of all sub-formulae provided herein, e. g. formulae I.1 andI.2, and to the intermediates such as compounds II, III, IV and V,wherein the substituents and variables (such as k, R¹, R², R³, R⁴, R⁵,R⁶, X, Y, Z, R^(A), R^(B), R^(a), R^(b) R^(c), R^(d) and R^(e)) haveindependently of each other or more preferably in combination (anypossible combination of 2 or more substituents as defined herein) thefollowing meanings:

Preference is also given to the uses, methods, mixtures andcompositions, wherein the definitions (such as phytopathogenic fungi,treatments, crops, compounds II, further active ingredients, solvents,solid carriers) have independently of each other or more preferably incombination the following meanings and even more preferably incombination (any possible combination of 2 or more definitions asprovided herein) with the preferred meanings of compounds I herein:

According to one embodiment of the invention, the invention also relatesto a method for combating phytopathogenic fungi containing a mutation inthe mitochondrial cytochrome b gene conferring resistance to Qoinhibitors, comprising: treating the phytopathogenic fungi containing amutation in the mitochondrial cytochrome b gene conferring resistance toQo inhibitors or the materials, plants, the soil or seeds that are atrisk of being diseased from phytopathogenic fungi containing a mutationin the mitochondrial cytochrome b gene conferring resistance to Qoinhibitors with an effective amount of at least one compound I, or acomposition comprising it thereof.

The term “phytopathogenic fungi containing a mutation in themitochondrial cytochrome b gene conferring resistance to Qo inhibitors”is be understood that at least 10% of the fungal isolates to becontrolled contain a mutation in the mitochondrial cytochrome b geneconferring resistance to Qo inhibitors, more preferably at least 30%,even more preferably at least 50%, and most preferably at least 75% ofthe fungi, in particular between 90 and 100%.

It has been observed under field conditions that populations ofphytopathogenic fungi apparently consisting of non-resistant strains canreadily develop resistance. The compounds can be applied under suchconditions, too, in order to prevent the formation of resistance and thespread of resistant strains altogether. In this regard it is useful thatthey have strong activity against non-resistant phytopathogenic fungialso.

According to another embodiment, the method for combatingphytopathogenic fungi, comprises: a) identifying the phytopathogenicfungi containing a mutation in the mitochondrial cytochrome b geneconferring resistance to Qo inhibitors, or the materials, plants, thesoil or seeds that are at risk of being diseased from phytopathogenicfungi as defined herein, and b) treating said fungi or the materials,plants, the soil or seeds with an effective amount of at least onecompound I, or a composition comprising it thereof.

According to another embodiment of the invention, the invention alsorelates to a method for combating phytopathogenic fungi containing amutation in the mitochondrial cytochrome b gene conferring resistance toQo inhibitors, comprising: treating the phytopathogenic fungi whereof atleast 10% contain a mutation in the mitochondrial cytochrome b geneconferring resistance to Qo inhibitors or the materials, plants, thesoil or seeds that are at risk of being diseased from phytopathogenicfungi containing a mutation in the mitochondrial cytochrome b geneconferring resistance to Qo inhibitors with an effective amount of atleast one compound I, or a composition comprising it thereof; morepreferably at least 30%, even more preferably at least 50%, and mostpreferably at least 75% of the fungi contain a mutation in themitochondrial cytochrome b gene conferring resistance to Qo inhibitors.

According to one embodiment of the use and the method for combatingphytopathogenic fungi, wherein the mutation in the mitochondrialcytochrome b gene of the phytopathogenic fungi is G143A.

According to another embodiment, the phytopathogenic fungi are selectedfrom the group consisting of basidomycetes, ascomycetes, and oomycetes.

According to a further embodiment, the phytopathogenic fungi areselected from the group consisting of Alternaria alternata, Blumeriagraminis, Pyricularia oryzae (also known as Magnaporthe grisea),Septoria tritici (also known as Mycosphaerella graminicola),Mycosphaerella fifiensis, Venturia inaequalis, Pyrenophora teres,Pyrenophora tritici-repentis and Plasmopara viticola, in particularSeptoria tritici.

One embodiment of the invention relates to compounds I, wherein R¹ ishalogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy,C₂-C₆-alkynyl, C₃-C₆-cycloalkyl or C₃-C₆-cycloalkyl-C₁-C₄-alkyl, whereinthe aliphatic moieties of R¹ may carry 1, 2, 3 or up to the maximumnumber of identical or different groups R^(b) which independently of oneanother are selected from halogen, CN, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkyl and C₁-C₄-haloalkoxy; more preferably R¹ is halogen,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl orC₁-C₄-haloalkoxy-C₁-C₄-alkyl; even more preferably R¹ is halogen,C₁-C₄-alkyl, C₁-C₄-chloroalkyl, C₁-C₄-alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkylor C₁-C₄-haloalkoxy-C₁-C₄-alkyl; in particular C₁-C₄-alkyl.

According to another embodiment, if R⁴ is1-methoxycarbonyl-2-methoxy-ethen-1-yl (R4-2, wherein X is O), R¹ cannotbe CF₃.

According to a further embodiment, R² is hydrogen, halogen, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl orC₁-C₄-haloalkoxy-C₁-C₄-alkyl; more preferably R² is hydrogen, halogen,C₁-C₄-alkyl, C₁-C₄-alkoxy, or C₁-C₄-alkoxy-C₁-C₄-alkyl; even morepreferably R² is hydrogen, C₁-C₄-alkyl or C₁-C₄-alkoxy; in particularhydrogen.

According to a further embodiment, R² is halogen, C₁-C₄-alkyl,C₁-C₄-alkoxy, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy, C₂-C₆-alkynyl,C₃-C₆-cycloalkyl or C₃-C₆-cycloalkyl-C₁-C₄-alkyl, wherein the aliphaticmoieties of R² may carry 1, 2, 3 or up to the maximum number ofidentical or different groups R^(a) which independently of one anotherare selected from halogen, CN, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkyl and C₁-C₄-haloalkoxy.

According to a further embodiment, Z is hydrogen or methyl, inparticular methyl.

According to a further embodiment, Y is a divalent group selected from—OCH₂—, —CH₂—, —CH₂CH₂—, —C(CH₃)═N—O—CH₂—, —O—N═C(CH₃)—C(CH₃)═N—O—CH₂—and —C(═N—O—CH₃)—C(CH₃)═N—O—CH₂—; preferably —OCH₂—, —CH₂CH₂—,—C(CH₃)═N—O—CH₂—, —O—N═C(CH₃)—C(CH₃)═N—O—CH₂— or—C(═N—O—CH₃)—C(CH₃)═N—O—CH₂—, where the bond depicted on the left sideof the divalent group Y is attached to R³, and the bond depicted on theright side is attached to the carbon atom being substituted by R²; inparticular Y is —OCH₂, which compounds are of formula I.1:

According to a further embodiment, Y is —CH₂—, which compounds are offormula I.2:

According to a further embodiment, Y is —CH₂CH₂—, which compounds are offormula I.3:

According to a further embodiment, Y is —C(CH₃)═N—O—CH₂—, whichcompounds are of formula I.4:

According to a further embodiment, Y is —O—N═C(CH₃)—C(CH₃)═N—O—CH₂—,which compounds are of formula I.5:

According to a further embodiment, Y is —C(═N—O—CH₃)—C(CH₃)═N—O—CH₂—,which compounds are of formula I.6:

Particularly preferred embodiments of the invention relate to compoundsI, wherein the group Y is one of the following radicals Y-1 to Y-10,where the bond depicted on the left side of the divalent group Y isattached to R³, and the bond depicted on the right side is attached tothe carbon atom being substituted by R²:

No. Y Y-1 —OCH₂— Y-2 —CH₂— Y-3 —CH₂CH₂— Y-4 —C(CH₃)═N—O—CH₂— Y-5—O—N═C(CH₃)—C(CH₃)═N—O—CH₂— Y-6 —C(═N—O—CH3)—C(CH3)═N—O—CH₂— Y-7—CH₂—C(CH₃)═N—O—CH₂— Y-8 —C(═O)—C(CH₃)═N—O—CH₂— Y-9 —CH₂OCH₂— Y-10—CH═N—O—CH₂—

Particularly preferred embodiments of the invention relate to compoundsI, wherein the group Y is —OCH₂—.

According to a further embodiment, R³ is phenyl or a 3- to 10-memberedsaturated, partially unsaturated or aromatic mono- or bicyclicheterocyclyl wherein the ring member atoms of the heterocyclyl includebesides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group ofN, O and S, wherein R³ may carry 1, 2, 3, 4 or up to the maximumpossible number of identical or different groups R^(b) as definedherein; more preferably said 3- to 10-membered saturated, partiallyunsaturated or aromatic mono- or bicyclic heterocyclyl is a 5- to6-membered heteroaryl wherein the ring member atoms of the heteroarylinclude besides carbon atoms 1, 2 or 3 heteroatoms selected from thegroup of N, O and S.

According to a further embodiment, R³ is phenyl, wherein the phenyl maycarry 1, 2, 3, 4 or up to the maximum possible number of identical ordifferent groups R^(b) as defined herein.

According to a further embodiment, R³ is a 5-membered-heteroaryl,wherein the ring member atoms of the heterocyclyl include besides carbonatoms 1, 2 or 3 heteroatoms selected from the group of N, O and S,wherein the heteroaryl may carry 1, 2, 3, 4 or up to the maximumpossible number of identical or different groups R^(b) as definedherein; more preferably said heteroaryl is pyrazolyl, imidazolyl,oxazolyl, isoxazolyl, thiazolyl, 1,2,4-triazolyl, 1,2,4-oxadiazolyl,1,3,4-oxadiazolyl or 1,2,4-thiadiazolyl.

According to a further embodiment, R³ is pyrazolyl, imidazolyl,oxazolyl, isoxazolyl, thiazolyl, 1,2,4-triazolyl, 1,2,4-oxadiazolyl,1,3,4-oxadiazolyl or 1,2,4-thiadiazolyl, which is substituted by phenyl,wherein said phenyl may carry 1, 2, 3 or up to the maximum possiblenumber of identical or different groups R^(c), which may be the same ordifferent to any other R^(c), wherein R^(c) is halogen, C₁-C₄-alkyl,C₂-C₄-alkenyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkoxyimino-C₁-C₄-alkyl, phenyl or a 5-membered saturated,partially unsaturated or aromatic heterocyclyl which, in addition tocarbon atoms, contains one to three heteroatoms from the groupconsisting of N, O and S as ring members; and wherein the aforementionedheterocyclyl groups R^(c) are attached via a direct bond, an oxygen orsulfur atom and for their part may carry 1, 2, 3 or up to the maximumpossible number of identical or different groups R^(d) as definedherein.

According to a further embodiment, R³ is a 6-membered-heteroaryl,wherein the ring member atoms of the heterocyclyl include besides carbonatoms 1, 2 or 3 heteroatoms selected from the group of N, O and S,wherein the heteroaryl may carry 1, 2, 3, 4 or up to the maximumpossible number of identical or different groups R^(b) as definedherein; more preferably said heteroaryl is pyridinyl or pyrimidinyl.

According to a further embodiment, R³ carries 1, 2 or 3 identical ordifferent groups R^(b).

According to a further embodiment, R^(b) independently of one anotherare selected from carboxyl, C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylamino,C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylcarbonyloxy, phenyl, naphthyl or a 3-to 10-membered saturated, partially unsaturated or aromatic mono- orbicyclic heterocyclyl which, in addition to carbon atoms, contains oneto four heteroatoms from the group consisting of O, N and S as ringmembers; and wherein the aforementioned phenyl and heterocyclyl groupsR^(b) are attached via a direct bond, an oxygen or sulfur atom.

According to a further embodiment, the aliphatic or cyclic groups R^(b)for their part carry 1, 2, 3 or up to the maximum possible number ofidentical or different groups R^(c), which, may be the same or differentto any other R^(c), selected from halogen, hydroxyl, nitro, CN,carboxyl, C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₈-alkynyl, C₁-C₄-haloalkyl,C₁-C₄-alkoxy and C₁-C₄-haloalkoxy; more preferably R^(b) for their partcarry 1, 2 or 3 identical or different groups R^(c).

According to a further embodiment, R^(c), which, may be the same ordifferent to any other R^(c), is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl,C₁-C₄-alkoxyimino-C₁-C₄-alkyl, phenyl or a 5-membered saturated,partially unsaturated or aromatic heterocyclyl which, in addition tocarbon atoms, contains one to three heteroatoms from the groupconsisting of N, O and S as ring members; wherein the aforementionedcyclic groups R^(c) are attached via a direct bond, an oxygen or sulfuratom and for their part may carry 1, 2, 3 or up to the maximum possiblenumber of identical or different groups R^(d) as defined herein.

According to a further embodiment, two radicals R^(b) that are bound toadjacent ring member atoms of the cyclic group R³ form together withsaid ring member atoms a fused 5-, 6- or 7-membered saturated, partiallyunsaturated or aromatic cycle, which may be a carbocycle or heterocycle,wherein the ring member atoms of the fused heterocycle include besidescarbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, Oand S.

According to a further embodiment, R³ is CR^(A)═N—O—R^(B), wherein R^(A)is amino, hydroxyl, C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₃-C₆-cycloalkyl,C₃-C₆-cycloalkenyl, C₂-C₆-alkenyloxy, C₃-C₆-alkynyloxy,C₁-C₄-alkoxyimino-C₁-C₄-alkyl, C₁-C₄-alkylamino, C₁-C₄-alkoxycarbonyl,C₁-C₄-alkylcarbonyloxy, phenyl, naphthyl or a 3- to 10-memberedsaturated, partially unsaturated or aromatic mono- or bicyclicheterocyclyl which, in addition to carbon atoms, contains one to fourheteroatoms from the group consisting of O, N and S as ring members; andwherein the aforementioned phenyl and heterocyclyl groups R^(A) areattached via a direct bond, an oxygen or sulfur atom, where thealiphatic or cyclic groups R^(A) may carry 1, 2, 3 or up to the maximumpossible number of identical or different groups R^(e), which may be thesame or different to any other R^(e), is halogen, hydroxyl, nitro, CN,carboxyl, C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₈-alkynyl, C₁-C₄-haloalkyl,C₁-C₄-alkoxy or C₁-C₄-haloalkoxy.

According to a further embodiment, R³ is CR^(A)═N—O—R^(B), wherein R^(B)is hydroxyl, C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₁-C₄-haloalkyl,C₃-C₆-cycloalkyl, C₃-C₆-cycloalkenyl,C₁-C₄-alkoxyimino-C₁-C₄-alkylC₁-C₄-alkoxycarbonyl, phenyl, naphthyl or a3- to 10-membered saturated, partially unsaturated or aromatic mono- orbicyclic heterocyclyl which, in addition to carbon atoms, contains oneto four heteroatoms from the group consisting of O, N and S as ringmembers, where the aliphatic or cyclic groups R^(B) may carry 1, 2, 3 orup to the maximum possible number of identical or different groupsR^(e), which may be the same or different to any other R^(e), ishalogen, hydroxyl, nitro, CN, carboxyl, C₁-C₄-alkyl, C₂-C₄-alkenyl,C₂-C₈-alkynyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy.

More preferably R^(A) and R^(B), independently of each other, areC₁-C₄-alkyl which may carry 1, 2, 3 or up to the maximum possible numberof identical or different halogen; in particular R^(A) and R^(B) aremethyl.

According to a further embodiment, the aliphatic or cyclic groups R^(A)and/or R^(B) for their part may carry 1, 2, 3 or up to the maximumpossible number of identical or different groups R^(e), more preferablythey carry 0, 1 or 3 identical or different groups R^(e). According to afurther embodiment, R^(e), which may be the same or different to anyother R^(e), is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy orC₁-C₄-haloalkoxy.

According to a further embodiment, R⁴ is —C(═NOCH₃)—CONHCH₃,—C(═NOCH₃)—COOCH₃, —C(═CHOCH₃)—COOCH₃, —C(═CHOCH₃)—CONHCH₃,—N(OCH₃)—COOCH₃, —N(CH₃)—COOCH₃ or —N(CH₂CH₃)—COOCH₃

According to a further embodiment, R⁴ is R4-1 as defined herein, whereinX is O.

According to a further embodiment, R⁴ is R4-1 as defined herein, whereinX is NH.

According to a further embodiment, R⁴ is R4-2 as defined herein, whereinX is O.

According to a further embodiment, R⁴ is R4-2 as defined herein, whereinX is NH.

According to a further embodiment, R⁴ is R4-3 as defined herein, whereinX is O.

According to a further embodiment, R⁴ is R4-3 as defined herein, whereinX is NH.

According to a further embodiment, R⁴ is R4-4 as defined herein, whereinX is O.

According to a further embodiment, R⁴ is R4-4 as defined herein, whereinX is NH.

According to a further embodiment, R⁵ is C₁-C₄-alkyl, C₁-C₄-haloalkyl,C₁-C₄-alkoxy or C₁-C₄-haloalkoxy, more preferably C₁-C₂-alkyl orC₁-C₂-alkoxy, even more preferably methyl, ethyl or methoxy.

According to a further embodiment, R⁴ is R4-4 as defined herein, whereinX is O and wherein R⁵ is methyl, ethyl or methoxy.

According to a further embodiment, R⁴ is R4-5 as defined herein, whereinX is O.

According to a further embodiment, R⁴ is R4-5 as defined herein, whereinX is NH.

According to a further embodiment, R⁴ is R4-6 as defined herein.

According to a further embodiment, R⁴ is R4-7 as defined herein.

Further embodiments of the invention relate to compounds I, wherein thegroup R³ is one of the following radicals R3-A to R3-B, wherein #indicates the point of attachment to the linker moiety Y:

Line R³ R3-A

R3-B

Particularly preferred embodiments of the invention relate to compoundsI, wherein the group R³ is one of the following radicals R3-1 to R3-195,wherein # indicates the point of attachment to the linker moiety Y:

TABLE A Line R³ R3-1 

R3-2 

R3-3 

R3-4 

R3-5 

R3-6 

R3-7 

R3-8 

R3-9 

R3-10 

R3-11 

R3-12 

R3-13 

R3-14 

R3-15 

R3-16 

R3-17 

R3-18 

R3-19 

R3-20 

R3-21 

R3-22 

R3-23 

R3-24 

R3-25 

R3-26 

R3-27 

R3-28 

R3-29 

R3-30 

R3-31 

R3-32 

R3-33 

R3-34 

R3-35 

R3-36 

R3-37 

R3-38 

R3-39 

R3-40 

R3-41 

R3-42 

R3-43 

R3-44 

R3-45 

R3-46 

R3-47 

R3-48 

R3-49 

R3-50 

R3-51 

R3-52 

R3-53 

R3-54 

R3-55 

R3-56 

R3-57 

R3-58 

R3-59 

R3-60 

R3-61 

R3-62 

R3-63 

R3-64 

R3-65 

R3-66 

R3-67 

R3-68 

R3-69 

R3-70 

R3-71 

R3-72 

R3-73 

R3-74 

R3-75 

R3-76 

R3-77 

R3-78 

R3-79 

R3-80 

R3-81 

R3-82 

R3-83 

R3-84 

R3-85 

R3-86 

R3-87 

R3-88 

R3-89 

R3-90 

R3-91 

R3-92 

R3-93 

R3-94 

R3-95 

R3-96 

R3-97 

R3-98 

R3-99 

R3-100

R3-101

R3-102

R3-103

R3-104

R3-105

R3-106

R3-107

R3-108

R3-109

R3-110

R3-111

R3-112

R3-113

R3-114

R3-115

R3-116

R3-117

R3-118

R3-119

R3-120

R3-121

R3-122

R3-123

R3-124

R3-125

R3-126

R3-127

R3-128

R3-129

R3-130

R3-131

R3-132

R3-133

R3-134

R3-135

R3-136

R3-137

R3-138

R3-139

R3-140

R3-141

R3-142

R3-143

R3-144

R3-145

R3-146

R3-147

R3-148

R3-149

R3-150

R3-151

R3-152

R3-153

R3-154

R3-155

R3-156

R3-157

R3-158

R3-159

R3-160

R3-161

R3-162

R3-163

R3-164

R3-165

R3-166

R3-167

R3-168

R3-169

R3-170

R3-171

R3-172

R3-173

R3-174

R3-175

R3-176

R3-177

R3-178

R3-179

R3-180

R3-181

R3-182

R3-183

R3-184

R3-185

R3-186

R3-187

R3-188

R3-189

R3-190

R3-191

R3-192

R3-193

R3-194

R3-195

wherein # indicates the point of attachment to the linker moiety Y.

Preferred embodiments of the invention relate to compounds I, whereinthe group R³ is R3-A, in particular R3-1(1-(4-chlorophenyl)-pyrazol-3-yl).

The compounds I and the compositions according to the invention,respectively, are suitable as fungicides. They are distinguished by anoutstanding effectiveness against a broad spectrum of phytopathogenicfungi, including soil-borne fungi, which derive especially from theclasses of the Plasmodiophoromycetes, Peronosporomycetes (syn.Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetesand Deuteromycetes (syn. Fungi imperfecti). Some are systemicallyeffective and they can be used in crop protection as foliar fungicides,fungicides for seed dressing and soil fungicides. Moreover, they aresuitable for controlling harmful fungi, which inter alia occur in woodor roots of plants.

The compounds I and the compositions according to the invention areparticularly important in the control of a multitude of phytopathogenicfungi on various cultivated plants, such as cereals, e. g. wheat, rye,barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet;fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears,plums, peaches, almonds, cherries, strawberries, raspberries,blackberries or gooseberries; leguminous plants, such as lentils, peas,alfalfa or soybeans; oil plants, such as rape, mustard, olives,sunflowers, coconut, cocoa beans, castor oil plants, oil palms, groundnuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiberplants, such as cotton, flax, hemp or jute; citrus fruit, such asoranges, lemons, grapefruits or mandarins; vegetables, such as spinach,lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes,cucurbits or paprika; lauraceous plants, such as avocados, cinnamon orcamphor; energy and raw material plants, such as corn, soybean, rape,sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines(table grapes and grape juice grape vines); hop; turf; sweet leaf (alsocalled Stevia); natural rubber plants or ornamental and forestry plants,such as flowers, shrubs, broad-leaved trees or evergreens, e. g.conifers; and on the plant propagation material, such as seeds, and thecrop material of these plants.

Preferably, compounds I and compositions thereof, respectively are usedfor controlling a multitude of fungi on field crops, such as potatoessugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton,soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits;vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans orsquashes.

The term “plant propagation material” is to be understood to denote allthe generative parts of the plant such as seeds and vegetative plantmaterial such as cuttings and tubers (e. g. potatoes), which can be usedfor the multiplication of the plant. This includes seeds, roots, fruits,tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants,including seedlings and young plants, which are to be transplanted aftergermination or after emergence from soil. These young plants may also beprotected before transplantation by a total or partial treatment byimmersion or pouring.

Preferably, treatment of plant propagation materials with compounds Iand compositions thereof, respectively, is used for controlling amultitude of fungi on cereals, such as wheat, rye, barley and oats;rice, corn, cotton and soybeans.

The term “cultivated plants” is to be understood as including plantswhich have been modified by breeding, mutagenesis or genetic engineeringincluding but not limiting to agricultural biotech products on themarket or in development (cf. cf. http://ceragmc.org/, see GM cropdatabase therein). Genetically modified plants are plants, which geneticmaterial has been so modified by the use of recombinant DNA techniquesthat under natural circumstances cannot readily be obtained by crossbreeding, mutations or natural recombination. Typically, one or moregenes have been integrated into the genetic material of a geneticallymodified plant in order to improve certain properties of the plant. Suchgenetic modifications also include but are not limited to targetedposttranslational modification of protein(s), oligo- or polypeptides e.g. by glycosylation or polymer additions such as prenylated, acetylatedor farnesylated moieties or PEG moieties.

The compounds I and compositions thereof, respectively, are particularlysuitable for controlling the following plant diseases:

Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. candida)and sunflowers (e. g. A. tragopogonis); Alternaria spp. (Alternaria leafspot) on vegetables, rape (A. brassicola or brassicae), sugar beets (A.tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A.alternata), tomatoes (e. g. A. solani or A. alternata) and wheat;Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. oncereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A.hordei on barley; Bipolaris and Drechslera spp. (teleomorph:Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northernleaf blight (B. zeicola) on corn, e. g. spot blotch (B. sorokiniana) oncereals and e.g. B. oryzae on rice and turfs; Blumeria (formerlyErysiphe) graminis (powdery mildew) on cereals (e. g. on wheat orbarley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: greymold) on fruits and berries (e. g. strawberries), vegetables (e. g.lettuce, carrots, celery and cabbages), rape, flowers, vines, forestryplants and wheat; Bremialactucae(downy mildew) on lettuce; Ceratocystis(syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees andevergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp.(Cercospora leaf spots) on corn (e.g. Gray leaf spot: C. zeae-maydis),rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee,soybeans (e. g. C. sofina or C. kikuchli) and rice; Cladosporium spp. ontomatoes (e. g. C. fulvum: leaf mold) and cereals, e. g. C. herbarum(black ear) on wheat; Claviceps purpurea (ergot) on cereals;Cochliobolus (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots)on corn (C. carbonum), cereals (e. g. C. sativus, anamorph: B.sorokiniana) and rice (e. g. C. miyabeanus, anamorph: H. oryzae);Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e.g. C. gossypi), corn (e. g. C. graminicola: Anthracnose stalk rot), softfruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C.lindemuthianum) and soybeans (e. g. C. truncatum or C. gloeosporioides);Corticium spp., e. g. C. sasakil (sheath blight) on rice; Corynesporacassilcola (leaf spots) on soybeans and ornamentals; Cycloconium spp.,e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit treecanker or young vine decline, teleomorph: Nectria or Neonectria spp.) onfruit trees, vines (e. g. C. liriodendri, teleomorph: Neonectrialiriodendri: Black Foot Disease) and ornamentals; Dematophora(teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans;Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans;Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. oncorn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e.g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback,apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F.mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremoniumchlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeriaobtusa; Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta:anthracnose) and vines (E. ampelina: anthracnose); Entyloma oryzae (leafsmut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp.(powdery mildew) on sugar beets (E. betae), vegetables (e. g. E. pisi),such as cucurbits (e. g. E. cichoracearum), cabbages, rape (e. g. E.cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph:Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines andornamental woods; Exserohllum(syn. Helminthosporium) spp. on corn (e. g.E. turcicum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stemrot) on various plants, such as F. graminearum or F. culmorum (root rot,scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum ontomatoes, F. solani on soybeans and F. verticillioides on corn;Gaeumannomyces graminis (take-all) on cereals (e. g. wheat or barley)and corn; Gibberella spp. on cereals (e. g. G. zeae) and rice (e. g. G.fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fruitsand other plants and G. gossypii on cotton; Grain-staining complex onrice; Guignardia bidwellii(black rot) on vines; Gymnosporangium spp. onrosaceous plants and junipers, e. g. G. sabinae (rust) on pears;Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) oncorn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leafrust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) onvines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) onsoybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snowmold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powderymildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M.fructigena (bloom and twig blight, brown rot) on stone fruits and otherrosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruitsand ground nuts, such as e. g. M. graminicola (anamorph: Septoriatritici, Septoria blotch) on wheat or M. fijiensis (black Sigatokadisease) on bananas; Peronospora spp. (downy mildew) on cabbage (e. g.P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor),tobacco (P. tabacina) and soybeans (e. g. P. manshurica); Phakopsorapachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp.e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans(e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rapeand cabbage and P. betae (root rot, leaf spot and damping-off) on sugarbeets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can andleaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph:Diaporthe phaseolorum); Physoderma maydis (brown spots) on corn;Phytophthora spp. (wilt, root, leaf, fruit and stem root) on variousplants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e.g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P.infestans: late blight) and broad-leaved trees (e. g. P. ramorum: suddenoak death); Plasmodiophora brassicae (club root) on cabbage, rape,radish and other plants; Plasmopara spp., e. g. P. viticola (grapevinedowny mildew) on vines and P. halstedii on sunflowers; Podosphaera spp.(powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g.P. leucotricha on apples; Polymyxa spp., e. g. on cereals, such asbarley and wheat (P. graminis) and sugar beets (P. betae) and therebytransmitted viral diseases; Pseudocercosporella herpotrichoides(eyespot, teleomorph: Tapesia yallundae) on cereals, e. g. wheat orbarley; Pseudoperonospora (downy mildew) on various plants, e. g. P.cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila(red fire disease or, rotbrenner′, anamorph: Phialophora) on vines;Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown orleaf rust), P. striiformis (stripe or yellow rust), P. hordei(dwarfrust), P. graminis (stem or black rust) or P. recondita (brown or leafrust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orangerust) on sugar cane and P. asparagi on asparagus; Pyrenophora (anamorph:Drechslera) tritici-repentis (tan spot) on wheat or P. teres (netblotch) on barley; Pyriculana spp., e. g. P. oryzae (teleomorph:Magnaporthe grisea, rice blast) on rice and P. grisea on turf andcereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton,rape, sunflowers, soybeans, sugar beets, vegetables and various otherplants (e. g. P. ultimum or P. aphanidermatum); Ramularia spp., e. g. R.collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barleyand R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice,potatoes, turf, corn, rape, potatoes, sugar beets, vegetables andvarious other plants, e. g. R. solani (root and stem rot) on soybeans,R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia springblight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot)on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporiumsecalis (scald) on barley, rye and triticale; Sarocladium oryzae and S.attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or whitemold) on vegetables and field crops, such as rape, sunflowers (e. g. S.sclerotiorum) and soybeans (e. g. S. rolfsii or S. sclerotiorum);Septoria spp. on various plants, e. g. S. glycines (brown spot) onsoybeans, S. tritici(Septoria blotch) on wheat and S. (syn.Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn.Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines;Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn.Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn,(e. g. S. reiliana: head smut), sorghum and sugar cane; Sphaerothecafuliginea (powdery mildew) on cucurbits; Spongospora subterranea(powdery scab) on potatoes and thereby transmitted viral diseases;Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch,teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat;Synchytrium endobioticum on potatoes (potato wart disease); Taphrinaspp., e. g. T. deformans (leaf curl disease) on peaches and T. pruni(plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco,pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn.Chalara elegans); Tilletia spp. (common bunt or stinking smut) oncereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T.controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) onbarley or wheat; Urocystis spp., e. g. U. occulta (stem smut) on rye;Uromyces spp. (rust) on vegetables, such as beans (e. g. U.appendiculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae);Ustliago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae),corn (e. g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab)on apples (e. g. V. inaequalis) and pears; and Verticillium spp. (wilt)on various plants, such as fruits and ornamentals, vines, soft fruits,vegetables and field crops, e. g. V. dahliae on strawberries, rape,potatoes and tomatoes.

The compounds I and compositions thereof, resepectively, may be used forimproving the health of a plant. The invention also relates to a methodfor improving plant health by treating a plant, its propagation materialand/or the locus where the plant is growing or is to grow with aneffective amount of compounds I and compositions thereof, respectively.

The term “plant health” is to be understood to denote a condition of theplant and/or its products which is determined by several indicatorsalone or in combination with each other such as yield (e. g. increasedbiomass and/or increased content of valuable ingredients), plant vigor(e. g. improved plant growth and/or greener leaves (“greening effect”)),quality (e. g. improved content or composition of certain ingredients)and tolerance to abiotic and/or biotic stress. The above identifiedindicators for the health condition of a plant may be interdependent ormay result from each other.

The compounds of formula I can be present in different crystalmodifications whose biological activity may differ. They are likewisesubject matter of the present invention.

The compounds I are employed as such or in form of compositions bytreating the fungi or the plants, plant propagation materials, such asseeds, soil, surfaces, materials or rooms to be protected from fungalattack with a fungicidally effective amount of the active substances.The application can be carried out both before and after the infectionof the plants, plant propagation materials, such as seeds, soil,surfaces, materials or rooms by the fungi.

Plant propagation materials may be treated with compounds I as such or acomposition comprising at least one compound I prophylactically eitherat or before planting or transplanting.

The invention also relates to agrochemical compositions comprising anauxiliary and at least one compound I according to the invention.

An agrochemical composition comprises a fungicidally effective amount ofa compound I. The term “effective amount” denotes an amount of thecomposition or of the compounds I, which is sufficient for controllingharmful fungi on cultivated plants or in the protection of materials andwhich does not result in a substantial damage to the treated plants.Such an amount can vary in a broad range and is dependent on variousfactors, such as the fungal species to be controlled, the treatedcultivated plant or material, the climatic conditions and the specificcompound I used.

The compounds I, their N-oxides and salts can be converted intocustomary types of agrochemical compositions, e. g. solutions,emulsions, suspensions, dusts, powders, pastes, granules, pressings,capsules, and mixtures thereof. Examples for composition types aresuspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC),emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes,pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS),pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG),insecticidal articles (e.g. LN), as well as gel formulations for thetreatment of plant propagation materials such as seeds (e.g. GF). Theseand further compositions types are defined in the “Catalogue ofpesticide formulation types and international coding system”, TechnicalMonograph No. 2, 6^(th) Ed. May 2008, CropLife International.

The compositions are prepared in a known manner, such as described byMollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001;or Knowles, New developments in crop protection product formulation,Agrow Reports DS243, T&F Informa, London, 2005.

Suitable auxiliaries are solvents, liquid carriers, solid carriers orfillers, surfactants, dispersants, emulsifiers, wetters, adjuvants,solubilizers, penetration enhancers, protective colloids, adhesionagents, thickeners, humectants, repellents, attractants, feedingstimulants, compatibilizers, bactericides, anti-freezing agents,anti-foaming agents, colorants, tackifiers and binders.

Suitable solvents and liquid carriers are water and organic solvents,such as mineral oil fractions of medium to high boiling point, e.g.kerosene, diesel oil; oils of vegetable or animal origin; aliphatic,cyclic and aromatic hydrocarbons, e. g. toluene, paraffin,tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol,propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones,e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acidesters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides,e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixturesthereof.

Suitable solid carriers or fillers are mineral earths, e.g. silicates,silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite,diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate,magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers,e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas;products of vegetable origin, e.g. cereal meal, tree bark meal, woodmeal, nutshell meal, and mixtures thereof.

Suitable surfactants are surface-active compounds, such as anionic,cationic, nonionic and amphoteric surfactants, block polymers,polyelectrolytes, and mixtures thereof. Such surfactants can be used asemusifier, dispersant, solubilizer, wetter, penetration enhancer,protective colloid, or adjuvant. Examples of surfactants are listed inMcCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon'sDirectories, Glen Rock, USA, 2008 (International Ed. or North AmericanEd.).

Suitable anionic surfactants are alkali, alkaline earth or ammoniumsalts of sulfonates, sulfates, phosphates, carboxylates, and mixturesthereof. Examples of sulfonates are alkylarylsulfonates,diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates,sulfonates of fatty acids and oils, sulfonates of ethoxylatedalkylphenols, sulfonates of alkoxylated arylphenols, sulfonates ofcondensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes,sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates orsulfosuccinamates. Examples of sulfates are sulfates of fatty acids andoils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols,or of fatty acid esters. Examples of phosphates are phosphate esters.Examples of carboxylates are alkyl carboxylates, and carboxylatedalcohol or alkylphenol ethoxylates.

Suitable nonionic surfactants are alkoxylates, N-substituted fatty acidamides, amine oxides, esters, sugar-based surfactants, polymericsurfactants, and mixtures thereof. Examples of alkoxylates are compoundssuch as alcohols, alkylphenols, amines, amides, arylphenols, fatty acidsor fatty acid esters which have been alkoxylated with 1 to 50equivalents. Ethylene oxide and/or propylene oxide may be employed forthe alkoxylation, preferably ethylene oxide. Examples of N-substitutedfatty acid amides are fatty acid glucamides or fatty acid alkanolamides.Examples of esters are fatty acid esters, glycerol esters ormonoglycerides. Examples of sugar-based surfactants are sorbitans,ethoxylated sorbitans, sucrose and glucose esters oralkylpolyglucosides. Examples of polymeric surfactants are home- orcopolymers of vinylpyrrolidone, vinyl-alcohols, or vinylacetate.

Suitable cationic surfactants are quaternary surfactants, for examplequaternary ammonium compounds with one or two hydrophobic groups, orsalts of long-chain primary amines. Suitable amphoteric surfactants arealkylbetains and imidazolines. Suitable block polymers are blockpolymers of the A-B or A-B-A type comprising blocks of polyethyleneoxide and polypropylene oxide, or of the A-B-C type comprising alkanol,polyethylene oxide and polypropylene oxide. Suitable polyelectrolytesare polyacids or polybases. Examples of polyacids are alkali salts ofpolyacrylic acid or polyacid comb polymers. Examples of polybases arepolyvinylamines or polyethyleneamines.

Suitable adjuvants are compounds, which have a neglectable or even nopesticidal activity themselves, and which improve the biologicalperformance of the compound I on the target. Examples are surfactants,mineral or vegetable oils, and other auxilaries. Further examples arelisted by Knowles, Adjuvants and additives, Agrow Reports DS256, T&FInforma UK, 2006, chapter 5.

Suitable thickeners are polysaccharides (e.g. xanthan gum,carboxymethylcellulose), anorganic clays (organically modified orunmodified), polycarboxylates, and silicates.

Suitable bactericides are bronopol and isothiazolinone derivatives suchas alkylisothiazolinones and benzisothiazolinones.

Suitable anti-freezing agents are ethylene glycol, propylene glycol,urea and glycerin.

Suitable anti-foaming agents are silicones, long chain alcohols, andsalts of fatty acids.

Suitable colorants (e.g. in red, blue, or green) are pigments of lowwater solubility and water-soluble dyes. Examples are inorganiccolorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) andorganic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).

Suitable tackifiers or binders are polyvinylpyrrolidons,polyvinylacetates, polyvinyl alcohols, polyacrylates, biological orsynthetic waxes, and cellulose ethers.

Examples for composition types and their preparation are:

i) Water-soluble concentrates (SL, LS)

10-60 wt % of a compound I and 5-15 wt % wetting agent (e.g. alcoholalkoxylates) are dissolved in water and/or in a water-soluble solvent(e.g. alcohols) ad 100 wt %. The active substance dissolves upondilution with water.

ii) Dispersible concentrates (DC)

5-25 wt % of a compound I and 1-10 wt % dispersant (e. g.polyvinylpyrrolidone) are dissolved in organic solvent (e.g.cyclohexanone) ad 100 wt %. Dilution with water gives a dispersion.

iii) Emulsifiable concentrates (EC)

15-70 wt % of a compound I and 5-10 wt % emulsifiers (e.g. calciumdodecylbenzenesulfonate and castor oil ethoxylate) are dissolved inwater-insoluble organic solvent (e.g. aromatic hydrocarbon) ad 100 wt %.Dilution with water gives an emulsion.

iv) Emulsions (EW, EO, ES)

5-40 wt % of a compound I and 1-10 wt % emulsifiers (e.g. calciumdodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in20-40 wt % water-insoluble organic solvent (e.g. aromatic hydrocarbon).This mixture is introduced into water ad 100 wt % by means of anemulsifying machine and made into a homogeneous emulsion. Dilution withwater gives an emulsion.

v) Suspensions (SC, OD, FS)

In an agitated ball mill, 20-60 wt % of a compound I are comminuted withaddition of 2-10 wt % dispersants and wetting agents (e.g. sodiumlignosulfonate and alcohol ethoxylate), 0.1-2 wt % thickener (e.g.xanthan gum) and water ad 100 wt % to give a fine active substancesuspension. Dilution with water gives a stable suspension of the activesubstance. For FS type composition up to 40 wt % binder (e.g.polyvinylalcohol) is added.

vi) Water-dispersible granules and water-soluble granules (WG, SG)

50-80 wt % of a compound I are ground finely with addition ofdispersants and wetting agents (e.g. sodium lignosulfonate and alcoholethoxylate) ad 100 wt % and prepared as water-dispersible orwater-soluble granules by means of technical appliances (e. g.extrusion, spray tower, fluidized bed). Dilution with water gives astable dispersion or solution of the active substance.

vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)

50-80 wt % of a compound I are ground in a rotor-stator mill withaddition of 1-5 wt % dispersants (e.g. sodium lignosulfonate), 1-3 wt %wetting agents (e.g. alcohol ethoxylate) and solid carrier (e.g. silicagel) ad 100 wt %. Dilution with water gives a stable dispersion orsolution of the active substance.

viii) Gel (GW, GF)

In an agitated ball mill, 5-25 wt % of a compound I are comminuted withaddition of 3-10 wt % dispersants (e.g. sodium lignosulfonate), 1-5 wt %thickener (e.g. carboxymethylcellulose) and water ad 100 wt % to give afine suspension of the active substance. Dilution with water gives astable suspension of the active substance.

iv) Microemulsion (ME)

5-20 wt % of a compound I are added to 5-30 wt % organic solvent blend(e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt % surfactantblend (e.g. alcohol ethoxylate and arylphenol ethoxylate), and water ad100%. This mixture is stirred for 1 h to produce spontaneously athermodynamically stable microemulsion.

iv) Microcapsules (CS)

An oil phase comprising 5-50 wt % of a compound I, 0-40 wt % waterinsoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt % acrylicmonomers (e.g. methylmethacrylate, methacrylic acid and a di- ortriacrylate) are dispersed into an aqueous solution of a protectivecolloid (e.g. polyvinyl alcohol). Radical polymerization initiated by aradical initiator results in the formation of poly(meth)acrylatemicrocapsules. Alternatively, an oil phase comprising 5-50 wt % of acompound I according to the invention, 0-40 wt % water insoluble organicsolvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g.diphenylmethene-4,4′-diisocyanatae) are dispersed into an aqueoussolution of a protective colloid (e.g. polyvinyl alcohol). The additionof a polyamine (e.g. hexamethylenediamine) results in the formation ofpolyurea microcapsules. The monomers amount to 1-10 wt %. The wt %relate to the total CS composition.

ix) Dustable powders (DP, DS)

1-10 wt % of a compound I are ground finely and mixed intimately withsolid carrier (e.g. finely divided kaolin) ad 100 wt %.

x) Granules (GR, FG)

0.5-30 wt % of a compound I is ground finely and associated with solidcarrier (e.g. silicate) ad 100 wt %. Granulation is achieved byextrusion, spray-drying or fluidized bed.

xi) Ultra-low volume liquids (UL)

1-50 wt % of a compound I are dissolved in organic solvent (e.g.aromatic hydrocarbon) ad 100 wt %.

The compositions types i) to xi) may optionally comprise furtherauxiliaries, such as 0.1-1 wt % bactericides, 5-15 wt % anti-freezingagents, 0.1-1 wt % anti-foaming agents, and 0.1-1 wt % colorants.

The agrochemical compositions generally comprise between 0.01 and 95%,preferably between 0.1 and 90%, and in particular between 0.5 and 75%,by weight of active substance. The active substances are employed in apurity of from 90% to 100%, preferably from 95% to 100% (according toNMR spectrum).

Solutions for seed treatment (LS), Suspoemulsions (SE), flowableconcentrates (FS), powders for dry treatment (DS), water-dispersiblepowders for slurry treatment (WS), water-soluble powders (SS), emulsions(ES), emulsifiable concentrates (EC) and gels (GF) are usually employedfor the purposes of treatment of plant propagation materials,particularly seeds. The compositions in question give, aftertwo-to-tenfold dilution, active substance concentrations of from 0.01 to60% by weight, preferably from 0.1 to 40%, in the ready-to-usepreparations. Application can be carried out before or during sowing.Methods for applying compound I and compositions thereof, respectively,on to plant propagation material, especially seeds include dressing,coating, pelleting, dusting, soaking and in-furrow application methodsof the propagation material. Preferably, compound I or the compositionsthereof, respectively, are applied on to the plant propagation materialby a method such that germination is not induced, e. g. by seeddressing, pelleting, coating and dusting.

When employed in plant protection, the amounts of active substancesapplied are, depending on the kind of effect desired, from 0.001 to 2 kgper ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.

In treatment of plant propagation materials such as seeds, e. g. bydusting, coating or drenching seed, amounts of active substance of from0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to100 g and most preferably from 5 to 100 g, per 100 kilogram of plantpropagation material (preferably seeds) are generally required.

When used in the protection of materials or stored products, the amountof active substance applied depends on the kind of application area andon the desired effect. Amounts customarily applied in the protection ofmaterials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of activesubstance per cubic meter of treated material.

Various types of oils, wetters, adjuvants, fertilizer, ormicronutrients, and further pesticides (e.g. herbicides, insecticides,fungicides, growth regulators, safeners) may be added to the activesubstances or the compositions comprising them as premix or, ifappropriate not until immediately prior to use (tank mix). These agentscan be admixed with the compositions according to the invention in aweight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

The user applies the composition according to the invention usually froma predosage device, a knapsack sprayer, a spray tank, a spray plane, oran irrigation system. Usually, the agrochemical composition is made upwith water, buffer, and/or further auxiliaries to the desiredapplication concentration and the ready-to-use spray liquor or theagrochemical composition according to the invention is thus obtained.Usually, 20 to 2000 liters, preferably 50 to 400 liters, of theready-to-use spray liquor are applied per hectare of agricultural usefularea.

According to one embodiment, individual components of the compositionaccording to the invention such as parts of a kit or parts of a binaryor ternary mixture may be mixed by the user himself in a spray tank andfurther auxiliaries may be added, if appropriate.

Mixing the compounds I or the compositions comprising them in the useform as fungicides with other fungicides results in many cases in anexpansion of the fungicidal spectrum of activity being obtained or in aprevention of fungicide resistance development. Furthermore, in manycases, synergistic effects are obtained.

The following list of active substances, in conjunction with which thecompounds I can be used, is intended to illustrate the possiblecombinations but does not limit them:

-   A) Respiration inhibitors    -   Inhibitors of complex III at Q_(o) site (e.g. strobilurins):        azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin,        enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin,        fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin,        picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin,        trifloxystrobin,        2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3-methoxy-acrylic acid        methyl ester and        2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)phenyl)-2-methoxyimino-N-methyl-acetamide,        pyribencarb, triclopyricarb/chlorodincarb, famoxadone,        fenamidone;    -   inhibitors of complex III at Qi site: cyazofamid, amisulbrom,        [(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate,        [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate,        [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate,        [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate;        (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl        2-methylpropanoate    -   inhibitors of complex II (e. g. carboxamides): benodanil,        benzovindiflupyr, bixafen, boscalid, carboxin, fenfuram,        fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam,        mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane,        tecloftalam, thifluzamide,        N-(4′-trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide,        N-(2-(1,3,3-trimethyl-butyl)-phenyl)-1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide,        3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide,        3-(trifluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide,        1,3-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide,        3-(trifluoromethyl)-1,5-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide,        3-(difluoromethyl)-1,5-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide,        1,3,5-trimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide;    -   other respiration inhibitors (e.g. complex I, uncouplers):        diflumetorim,        (5,8-difluoroquinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine;        nitrophenyl derivates: binapacryl, dinobuton, dinocap,        fluazinam; ferimzone; organometal compounds: fentin salts, such        as fentin-acetate, fentin chloride or fentin hydroxide;        ametoctradin; and silthiofam;-   B) Sterol biosynthesis inhibitors (SBI fungicides)    -   C14 demethylase inhibitors (DMI fungicides): triazoles:        azaconazole, bitertanol, bromuconazole, cyproconazole,        difenoconazole, diniconazole, diniconazole-M, epoxiconazole,        fenbuconazole, fluquinconazole, flusilazole, flutriafol,        hexaconazole, imibenconazole, ipconazole, metconazole,        myclobutanil, oxpoconazole, paclobutrazole, penconazole,        propiconazole, prothioconazole, simeconazole, tebuconazole,        tetraconazole, triadimefon, triadimenol, triticonazole,        uniconazole, 1-[rel-(2 S;        3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1H-[1,2,4]triazole,        2-[rel-(2S;        3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiranylmethyl]-2H-[1,2,4]triazole-3-thiol;        imidazoles: imazalil, pefurazoate, prochloraz, triflumizol;        pyrimidines, pyridines and piperazines: fenarimol, nuarimol,        pyrifenox, triforine;    -   Delta14-reductase inhibitors: aldimorph, dodemorph,        dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin,        piperalin, spiroxamine;    -   Inhibitors of 3-keto reductase: fenhexamid;-   C) Nucleic acid synthesis inhibitors    -   phenylamides or acyl amino acid fungicides: benalaxyl,        benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam),        ofurace, oxadixyl;    -   others: hymexazole, octhilinone, oxolinic acid, bupirimate,        5-fluorocytosine, 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine,        5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine;-   D) Inhibitors of cell division and cytoskeleton    -   tubulin inhibitors, such as benzimidazoles, thiophanates:        benomyl, carbendazim, fuberidazole, thiabendazole,        thiophanate-methyl; triazolopyrimidines:        5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine    -   other cell division inhibitors: diethofencarb, ethaboxam,        pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone;-   E) Inhibitors of amino acid and protein synthesis    -   methionine synthesis inhibitors (anilino-pyrimidines):        cyprodinil, mepanipyrim, pyrimethanil;    -   protein synthesis inhibitors: blasticidin-S, kasugamycin,        kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin,        oxytetracyclin, polyoxine, validamycin A;-   F) Signal transduction inhibitors    -   MAP/histidine kinase inhibitors: fluoroimid, iprodione,        procymidone, vinclozolin, fenpiclonil, fludioxonil;    -   G protein inhibitors: quinoxyfen;-   G) Lipid and membrane synthesis inhibitors    -   Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos,        pyrazophos, isoprothiolane;    -   lipid peroxidation: dicloran, quintozene, tecnazene,        tolclofos-methyl, biphenyl, chloroneb, etridiazole;    -   phospholipid biosynthesis and cell wall deposition:        dimethomorph, flumorph, mandipropamid, pyrimorph,        benthiavalicarb, iprovalicarb, valifenalate and        N-(1-(1-(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic        acid-(4-fluorophenyl) ester;    -   compounds affecting cell membrane permeability and fatty acides:        propamocarb, propamocarb-hydrochlorid    -   fatty acid amide hydrolase inhibitors:        1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone-   H) Inhibitors with Multi Site Action    -   inorganic active substances: Bordeaux mixture, copper acetate,        copper hydroxide, copper oxychloride, basic copper sulfate,        sulfur;    -   thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam,        metiram, propineb, thiram, zineb, ziram;    -   organochlorine compounds (e.g. phthalimides, sulfamides,        chloronitriles): anilazine, chlorothalonil, captafol, captan,        folpet, dichlofluanid, dichlorophen, flusulfamide,        hexachlorobenzene, pentachlorphenole and its salts, phthalide,        tolylfluanid,        N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;    -   guanidines and others: guanidine, dodine, dodine free base,        guazatine, guazatine-acetate, iminoctadine,        iminoctadine-triacetate, iminoctadine-tris(albesilate),        dithianon,        2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)tetraone;-   I) Cell wall synthesis inhibitors    -   inhibitors of glucan synthesis: validamycin, polyoxin B; melanin        synthesis inhibitors: pyroquilon, tricyclazole, carpropamid,        dicyclomet, fenoxanil;-   J) Plant defense inducers    -   acibenzolar-S-methyl, probenazole, isotianil, tiadinil,        prohexadione-calcium; phosphonates: fosetyl, fosetyl-aluminum,        phosphorous acid and its salts;-   K) Unknown mode of action    -   bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet,        debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate,        diphenylamin, fenpyrazamine, flumetover, flusulfamide,        flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl,        oxathiapiprolin, oxin-copper, proquinazid, tebufloquin,        tecloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen-4-one,        N-(cyclopropylmethoxyimino-(6-difluoromethoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl        acetamide,        N′-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl        formamidine,        N′-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl        formamidine,        N′-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl        formamidine,        N′-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl        formamidine, methoxy-acetic acid        6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester,        3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine,        3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine        (pyrisoxazole), N-(6-methoxy-pyridin-3-yl)        cyclopropanecarboxylic acid amide,        5-chloro-1-(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1H-benzoimidazole,        2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;-   L) Antifungal biocontrol agents, plant bioactivators: Ampelomyces    quisqualis (e.g. AQ 10® from Intrachem Bio GmbH & Co. KG, Germany),    Aspergillus flavus (e.g. AFLAGUARD® from Syngenta, CH),    Aureobasidium pullulans (e.g. BOTECTOR® from bio-ferm GmbH,    Germany), Bacillus pumilus (e.g. NRRL Accession No. B-30087 in    SONATA® and BALLAD® Plus from AgraQuest Inc., USA), Bacillus    subtilis(e.g. isolate NRRL-Nr. B-21661 in RHAPSODY®, SERENADE® MAX    and SERENADE® ASO from AgraQuest Inc., USA), Bacillus subtilis var.    amyloliquefaciens FZB24 (e.g. TAEGRO® from Novozyme Biologicals,    Inc., USA), Candida oleophila I-82 (e.g. ASPIRE® from Ecogen Inc.,    USA), Candida saitoana (e.g. BIOCURE® (in mixture with lysozyme) and    BIOCOAT® from Micro Flo Company, USA (BASF SE) and Arysta), Chitosan    (e.g. ARMOUR-ZEN from BotriZen Ltd., NZ), Clonostachys rosea f.    catenulata, also named Gliocladium catenulatum (e.g. isolate J1446:    PRESTOP® from Verdera, Finland), Coniothyrium minitans (e.g.    CONTANS® from Prophyta, Germany), Cryphonectria parasitica (e.g.    Endothia parasitica from CNICM, France), Cryptococcus albidus (e.g.    YIELD PLUS® from Anchor Bio-Technologies, South Africa), Fusarium    oxysporum (e.g. BIOFOX® from S.I.A.P.A., Italy, FUSACLEAN® from    Natural Plant Protection, France), Metschnikowia fructicola (e.g.    SHEMER® from Agrogreen, Israel), Microdochium dimerum (e.g. ANTIBOT®    from Agrauxine, France), Phlebiopsis gigantea (e.g. ROTSOP® from    Verdera, Finland), Pseudozyma flocculosa (e.g. SPORODEX® from Plant    Products Co. Ltd., Canada), Pythium oligandrum DV74 (e.g.    POLYVERSUM® from Remeslo SSRO, Biopreparaty, Czech Rep.), Reynoutria    sachlinensis (e.g. REGALIA® from Marrone Biolnnovations, USA),    Talaromyces flavus V117b (e.g. PROTUS® from Prophyta, Germany),    Trichoderma asperellum SKT-1 (e.g. ECO-HOPE® from Kumiai Chemical    Industry Co., Ltd., Japan), T. atroviride LC52 (e.g. SENTINEL® from    Agrimm Technologies Ltd, NZ), T. harzianum T-22 (e.g. PLANTSHIELD®    der Firma BioWorks Inc., USA), T. harzianum TH 35 (e.g. ROOT PRO®    from Mycontrol Ltd., Israel), T. harzianum T-39 (e.g. TRICHODEX® and    TRICHODERMA 2000® from Mycontrol Ltd., Israel and Makhteshim Ltd.,    Israel), T. harzianum and T. viride (e.g. TRICHOPEL from Agrimm    Technologies Ltd, NZ), T. harzianum ICC012 and T. viride ICC080    (e.g. REMEDIER® WP from Isagro Ricerca, Italy), T. polysporum and T.    harzianum (e.g. BINAB® from BINAB Bio-Innovation AB, Sweden), T.    stromaticum (e.g. TRICOVAB® from C.E.P.L.A.C., Brazil), T. virens    GL-21 (e.g. SOILGARD® from Certis LLC, USA), T. viride (e.g. TRIECO®    from Ecosense Labs. (India) Pvt. Ltd., Indien, BIO-CURE® F from T.    Stanes & Co. Ltd., Indien), T. viride TV1 (e.g. T. viride TV1 from    Agribiotec srl, Italy), Ulocladium oudemansii HRU3 (e.g. BOTRY-ZEN®    from Botry-Zen Ltd, NZ);-   M) Growth regulators    -   abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine,        brassinolide, butralin, chlormequat (chlormequat chloride),        choline chloride, cyclanilide, daminozide, dikegulac,        dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin,        flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid,        inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide,        mepiquat (mepiquat chloride), naphthaleneacetic acid,        N-6-benzyladenine, paclobutrazol, prohexadione        (prohexadione-calcium), prohydrojasmon, thidiazuron,        triapenthenol, tributyl phosphorotrithioate,        2,3,5-tri-iodobenzoic acid, trinexapac-ethyl and uniconazole;-   N) Herbicides    -   acetamides: acetochlor, alachlor, butachlor, dimethachlor,        dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor,        napropamide, naproanilide, pethoxamid, pretilachlor, propachlor,        thenylchlor;    -   amino acid derivatives: bilanafos, glyphosate, glufosinate,        sulfosate;    -   aryloxyphenoxypropionates: clodinafop, cyhalofop-butyl,        fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop,        quizalofop, quizalofop-P-tefuryl;    -   Bipyridyls: diquat, paraquat;    -   (thio)carbamates: asulam, butylate, carbetamide, desmedipham,        dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb,        phenmedipham, prosulfocarb, pyributicarb, thiobencarb,        triallate;    -   cyclohexanediones: butroxydim, clethodim, cycloxydim,        profoxydim, sethoxydim, tepraloxydim, tralkoxydim;    -   dinitroanilines: benfluralin, ethalfluralin, oryzalin,        pendimethalin, prodiamine, trifluralin;    -   diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop,        ethoxyfen, fomesafen, lactofen, oxyfluorfen;    -   hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil;    -   imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr,        imazaquin, imazethapyr;    -   phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid        (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB,        Mecoprop;    -   pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet,        norflurazon, pyridate;    -   pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr,        fluridone, fluroxypyr, picloram, picolinafen, thiazopyr;    -   sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron,        chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron,        ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron,        foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron,        mesosulfuron, metazosulfuron, metsulfuron-methyl, nicosulfuron,        oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron,        rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron,        triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron,        tritosulfuron,        1-((2-chloro-6-propyl-imidazo[1,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6-dimethoxypyrimidin-2-yl)urea;    -   triazines: ametryn, atrazine, cyanazine, dimethametryn,        ethiozin, hexazinone, metamitron, metribuzin, prometryn,        simazine, terbuthylazine, terbutryn, triaziflam;    -   ureas: chlorotoluron, daimuron, diuron, fluometuron,        isoproturon, linuron, methabenzthiazuron, tebuthiuron;    -   other acetolactate synthase inhibitors: bispyribac-sodium,        cloransulam-methyl, diclosulam, florasulam, flucarbazone,        flumetsulam, metosulam, ortho-sulfamuron, penoxsulam,        propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid,        pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfone,        pyroxsulam;    -   others: amicarbazone, aminotriazole, anilofos, beflubutamid,        benazolin, bencarbazone, benfluresate, benzofenap, bentazone,        benzobicyclon, bicyclopyrone, bromacil, bromobutide,        butafenacil, butamifos, cafenstrole, carfentrazone,        cinidon-ethyl, chlorthal, cinmethylin, clomazone, cumyluron,        cyprosulfamide, dicamba, difenzoquat, diflufenzopyr, Drechslera        monoceras, endothal, ethofumesate, etobenzanid, fenoxasulfone,        fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam,        flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole,        lenacil, propanil, propyzamide, quinclorac, quinmerac,        mesotrione, methyl arsonic acid, naptalam, oxadiargyl,        oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil,        pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate,        quinoclamine, saflufenacil, sulcotrione, sulfentrazone,        terbacil, tefuryltrione, tembotrione, thiencarbazone,        topramezone,        (3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)-phenoxy]-pyridin-2-yloxy)-acetic        acid ethyl ester,        6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid        methyl ester,        6-chloro-3-(2-cyclopropyl-6-methyl-phenoxy)-pyridazin-4-ol,        4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2-carboxylic        acid,        4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)-pyridine-2-carboxylic        acid methyl ester, and        4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluoro-phenyl)-pyridine-2-carboxylic        acid methyl ester.-   O) Insecticides    -   organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl,        chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon,        dichlorvos, dicrotophos, dimethoate, disulfoton, ethion,        fenitrothion, fenthion, isoxathion, malathion, methamidophos,        methidathion, methyl-parathion, mevinphos, monocrotophos,        oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone,        phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl,        profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos,        triazophos, trichlorfon;    -   carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb,        carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb,        methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb,        triazamate;    -   pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin,        cyphenothrin, cypermethrin, alpha-cypermethrin,        beta-cypermethrin, zeta-cypermethrin, deltamethrin,        esfenvalerate, etofenprox, fenpropathrin, fenvalerate,        imiprothrin, lambda-cyhalothrin, permethrin, prallethrin,        pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate,        tefluthrin, tetramethrin, tralomethrin, transfluthrin,        profluthrin, dimefluthrin;    -   insect growth regulators: a) chitin synthesis inhibitors:        benzoylureas: chlorfluazuron, cyramazin, diflubenzuron,        flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron,        teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox,        etoxazole, clofentazine; b) ecdysone antagonists: halofenozide,        methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids:        pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis        inhibitors: spirodiclofen, spiromesifen, spirotetramat;    -   nicotinic receptor agonists/antagonists compounds: clothianidin,        dinotefuran, flupyradifurone, imidacloprid, thiamethoxam,        nitenpyram, acetamiprid, thiacloprid,        1-2-chloro-thiazol-5-ylmethyl)-2-nitrimino-3,5-dimethyl-[1,3,5]triazinane;    -   GABA antagonist compounds: endosulfan, ethiprole, fipronil,        vaniliprole, pyrafluprole, pyriprole,        5-amino-1-(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl-1H-pyrazole-3-carbothioic        acid amide;    -   macrocyclic lactone insecticides: abamectin, emamectin,        milbemectin, lepimectin, spinosad, spinetoram;    -   mitochondrial electron transport inhibitor (METI) I acaricides:        fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;    -   METI II and III compounds: acequinocyl, fluacyprim,        hydramethylnon;    -   Uncouplers: chlorfenapyr;    -   oxidative phosphorylation inhibitors: cyhexatin, diafenthiuron,        fenbutatin oxide, propargite;    -   moulting disruptor compounds: cryomazine;    -   mixed function oxidase inhibitors: piperonyl butoxide;    -   sodium channel blockers: indoxacarb, metaflumizone;    -   others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl,        pymetrozine, sulfur, thiocyclam, flubendiamide,        chlorantraniliprole, cyazypyr (HGW86), cyenopyrafen,        flupyrazofos, cyflumetofen, amidoflumet, imicyafos,        bistrifluron, and pyrifluquinazon.

The present invention furthermore relates to agrochemical compositionscomprising a mixture of at least one compound I (component 1) and atleast one further active substance useful for plant protection, e. g.selected from the groups A) to O) (component 2), in particular onefurther fungicide, e. g. one or more fungicide from the groups A) to L),as described above, and if desired one suitable solvent or solidcarrier. Those mixtures are of particular interest, since many of themat the same application rate show higher efficiencies against harmfulfungi. Furthermore, combating harmful fungi with a mixture of compoundsI and at least one fungicide from groups A) to L), as described above,is more efficient than combating those fungi with individual compounds Ior individual fungicides from groups A) to L). By applying compounds Itogether with at least one active substance from groups A) to O) asynergistic effect can be obtained, i.e. more then simple addition ofthe individual effects is obtained (synergistic mixtures).

This can be obtained by applying the compounds I and at least onefurther active substance simultaneously, either jointly (e. g. astank-mix) or seperately, or in succession, wherein the time intervalbetween the individual applications is selected to ensure that theactive substance applied first still occurs at the site of action in asufficient amount at the time of application of the further activesubstance(s). The order of application is not essential for working ofthe present invention.

In binary mixtures, i.e. compositions according to the inventioncomprising one compound I (component 1) and one further active substance(component 2), e. g. one active substance from groups A) to O), theweight ratio of component 1 and component 2 generally depends from theproperties of the active substances used, usually it is in the range offrom 1:100 to 100:1, regularly in the range of from 1:50 to 50:1,preferably in the range of from 1:20 to 20:1, more preferably in therange of from 1:10 to 10:1 and in particular in the range of from 1:3 to3:1.

In ternary mixtures, i.e. compositions according to the inventioncomprising one compound I (component 1) and a first further activesubstance (component 2) and a 35 second further active substance(component 3), e. g. two active substances from groups A) to 0), theweight ratio of component 1 and component 2 depends from the propertiesof the active substances used, preferably it is in the range of from1:50 to 50:1 and particularly in the range of from 1:10 to 10:1, and theweight ratio of component 1 and component 3 preferably is in the rangeof from 1:50 to 50:1 and particularly in the range of from 1:10 to 10:1.

Preference is also given to mixtures comprising a compound I(component 1) and at least one active substance selected from group A)(component 2) and particularly selected from azoxystrobin,dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin,picoxystrobin, pyraclostrobin, trifloxystrobin; famoxadone, fenamidone;benzovindiflupyr, bixafen, boscalid, fluopyram, fluxapyroxad,isopyrazam, penflufen, penthiopyrad, sedaxane; ametoctradin, cyazofamid,fluazinam, fentin salts, such as fentin acetate.

Preference is given to mixtures comprising a compound of formula I(component 1) and at least one active substance selected from group B)(component 2) and particularly selected from cyproconazole,difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol,metconazole, myclobutanil, penconazole, propiconazole, prothioconazole,triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole,prochloraz, fenarimol, triforine; dodemorph, fenpropimorph, tridemorph,fenpropidin, spiroxamine; fenhexamid.

Preference is given to mixtures comprising a compound of formula I(component 1) and at least one active substance selected from group C)(component 2) and particularly selected from metalaxyl, (metalaxyl-M)mefenoxam, ofurace.

Preference is given to mixtures comprising a compound of formula I(component 1) and at least one active substance selected from group D)(component 2) and particularly selected from benomyl, carbendazim,thiophanate-methyl, ethaboxam, fluopicolide, zoxamide, metrafenone,pyriofenone.

Preference is also given to mixtures comprising a compound I(component 1) and at least one active substance selected from group E)(component 2) and particularly selected from cyprodinil, mepanipyrim,pyrimethanil.

Preference is also given to mixtures comprising a compound I(component 1) and at least one active substance selected from group F)(component 2) and particularly selected from iprodione, fludioxonil,vinclozolin, quinoxyfen.

Preference is also given to mixtures comprising a compound I(component 1) and at least one active substance selected from group G)(component 2) and particularly selected from dimethomorph, flumorph,iprovalicarb, benthiavalicarb, mandipropamid, propamocarb.

Preference is also given to mixtures comprising a compound I(component 1) and at least one active substance selected from group H)(component 2) and particularly selected from copper acetate, copperhydroxide, copper oxychloride, copper sulfate, sulfur, mancozeb,metiram, propineb, thiram, captafol, folpet, chlorothalonil,dichlofluanid, dithianon.

Preference is also given to mixtures comprising a compound I(component 1) and at least one active substance selected from group I)(component 2) and particularly selected from carpropamid and fenoxanil.

Preference is also given to mixtures comprising a compound I(component 1) and at least one active substance selected from group J)(component 2) and particularly selected from acibenzolar-S-methyl,probenazole, tiadinil, fosetyl, fosetyl-aluminium, H₃PO₃ and saltsthereof.

Preference is also given to mixtures comprising a compound I(component 1) and at least one active substance selected from group K)(component 2) and particularly selected from cymoxanil, proquinazid andN-methyl-2-{1-[(5-methyl-3-trifluoromethyl-1H-pyrazol-1-yl)-acetyl]-piperidin-4-yl}-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]-4-thiazolecarboxamide.

Preference is also given to mixtures comprising a compound I(component 1) and at least one active substance selected from group L)(component 2) and particularly selected from Bacillus subtilis strainNRRL No. B-21661, Bacillus pumilus strain NRRL No. B-30087 andUlocladium oudemansii.

Accordingly, the present invention furthermore relates to compositionscomprising one compound I (component 1) and one further active substance(component 2), which further active substance is selected from thecolumn “Component 2” of the lines B-1 to B-369 of Table B.

A further embodiment relates to the compositions B-1 to B-369 listed inTable B, where a row of Table B corresponds in each case to a fungicidalcomposition comprising one of the in the present specificationindividualized compounds of formula I (component 1) and the respectivefurther active substance from groups A) to O) (component 2) stated inthe row in question. Preferably, the compositions described comprise theactive substances in synergistically effective amounts.

TABLE B Composition comprising one indiviualized compound I and onefurther active substance from groups A) to O) Mixture Component 1Component 2 B-1 one individualized Azoxystrobin compound I B-2 oneindividualized Coumethoxystrobin compound I B-3 one individualizedCoumoxystrobin compound I B-4 one individualized Dimoxystrobin compoundI B-5 one individualized Enestroburin compound I B-6 one individualizedFenaminstrobin compound I B-7 one individualizedFenoxystrobin/Flufenoxystrobin compound I B-8 one individualizedFluoxastrobin compound I B-9 one individualized Kresoxim-methyl compoundI B-10 one individualized Metominostrobin compound I B-11 oneindividualized Orysastrobin compound I B-12 one individualizedPicoxystrobin compound I B-13 one individualized Pyraclostrobin compoundI B-14 one individualized Pyrametostrobin compound I B-15 oneindividualized Pyraoxystrobin compound I B-16 one individualizedPyribencarb compound I B-17 one individualized Trifloxystrobin compoundI B-18 one individualized Triclopyricarb/Chlorodincarb compound I B-19one individualized 2-[2-(2,5-dimethyl-phenoxymethyl)- compound Iphenyl]-3-methoxy-acrylic acid methyl ester B-20 one individualized2-(2-(3-(2,6-dichlorophenyl)-1-methyl- compound Iallylideneaminooxymethyl)-phenyl)- 2-methoxyimino-N-methyl-acetamideB-21 one individualized Benalaxyl compound I B-22 one individualizedBenalaxyl-M compound I B-23 one individualized Benodanil compound I B-24one individualized Benzovindiflupyr compound I B-25 one individualizedBixafen compound I B-26 one individualized Boscalid compound I B-27 oneindividualized Carboxin compound I B-28 one individualized Fenfuramcompound I B-29 one individualized Fenhexamid compound I B-30 oneindividualized Flutolanil compound I B-31 one individualizedFluxapyroxad compound I B-32 one individualized Furametpyr compound IB-33 one individualized Isopyrazam compound I B-34 one individualizedIsotianil compound I B-35 one individualized Kiralaxyl compound I B-36one individualized Mepronil compound I B-37 one individualized Metalaxylcompound I B-38 one individualized Metalaxyl-M compound I B-39 oneindividualized Ofurace compound I B-40 one individualized Oxadixylcompound I B-41 one individualized Oxycarboxin compound I B-42 oneindividualized Penflufen compound I B-43 one individualized Penthiopyradcompound I B-44 one individualized Sedaxane compound I B-45 oneindividualized Tecloftalam compound I B-46 one individualizedThifluzamide compound I B-47 one individualized Tiadinil compound I B-48one individualized 2-Amino-4-methyl-thiazole-5-carboxylic compound Iacid anilide B-49 one individualizedN-(4′-trifluoromethylthiobiphenyl-2-yl)- compound I3-difluoromethyl-1-methyl-1H-pyrazole- 4-carboxamide B-50 oneindividualized N-(2-(1,3,3-trimethyl-butyl)-phenyl)- compound I1,3-dimethyl-5-fluoro-1H-pyrazole- 4-carboxamide B-51 one individualized3-(difluoromethyl)-1-methyl-N-(1,1,3-tri- compound Imethylindan-4-yl)pyrazole-4-carbox- amide B-52 one individualized3-(trifluoromethyl)-1-methyl-N-(1,1,3-tri- compound Imethylindan-4-yl)pyrazole-4-carbox- amide B-53 one individualized1,3-dimethyl-N-(1,1,3-trimethylindan- compound I4-yl)pyrazole-4-carboxamide B-54 one individualized3-(trifluoromethyl)-1,5-dimethyl- compound IN-(1,1,3-trimethylindan-4-yl)pyrazole- 4-carboxamide B-55 oneindividualized 3-(difluoromethyl)-1,5-dimethyl- compound IN-(1,1,3-trimethylindan-4-yl)pyrazole- 4-carboxamide B-56 oneindividualized 1,3,5-trimethyl-N-(1,1,3-trimethylindan- compound I4-yl)pyrazole-4-carboxamide B-57 one individualized Dimethomorphcompound I B-58 one individualized Flumorph compound I B-59 oneindividualized Pyrimorph compound I B-60 one individualized Flumetovercompound I B-61 one individualized Fluopicolide compound I B-62 oneindividualized Fluopyram compound I B-63 one individualized Zoxamidecompound I B-64 one individualized Carpropamid compound I B-65 oneindividualized Diclocymet compound I B-66 one individualizedMandipropamid compound I B-67 one individualized Oxytetracyclin compoundI B-68 one individualized Silthiofam compound I B-69 one individualizedN-(6-methoxy-pyridin-3-yl) cyclopro- compound I panecarboxylic acidamide B-70 one individualized Azaconazole compound I B-71 oneindividualized Bitertanol compound I B-72 one individualizedBromuconazole compound I B-73 one individualized Cyproconazole compoundI B-74 one individualized Difenoconazole compound I B-75 oneindividualized Diniconazole compound I B-76 one individualizedDiniconazole-M compound I B-77 one individualized Epoxiconazole compoundI B-78 one individualized Fenbuconazole compound I B-79 oneindividualized Fluquinconazole compound I B-80 one individualizedFlusilazole compound I B-81 one individualized Flutriafol compound IB-82 one individualized Hexaconazol compound I B-83 one individualizedImibenconazole compound I B-84 one individualized Ipconazole compound IB-85 one individualized Metconazole compound I B-86 one individualizedMyclobutanil compound I B-87 one individualized Oxpoconazol compound IB-88 one individualized Paclobutrazol compound I B-89 one individualizedPenconazole compound I B-90 one individualized Propiconazole compound IB-91 one individualized Prothioconazole compound I B-92 oneindividualized Simeconazole compound I B-93 one individualizedTebuconazole compound I B-94 one individualized Tetraconazole compound IB-95 one individualized Triadimefon compound I B-96 one individualizedTriadimenol compound I B-97 one individualized Triticonazole compound IB-98 one individualized Uniconazole compound I B-99 one individualized1-[rel-(2S;3R)-3-(2-chlorophenyl)- compound I2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1H-[1,2,4]triazole, B-100 one individualized2-[rel-(2S;3R)-3-(2-chlorophenyl)- compound I2-(2,4-difluorophenyl)-oxiranylmethyl]- 2H-[1,2,4]triazole-3-thiol B-101one individualized Cyazofamid compound I B-102 one individualizedAmisulbrom compound I B-103 one individualized Imazalil compound I B-104one individualized Imazalil-sulfate compound I B-105 one individualizedPefurazoate compound I B-106 one individualized Prochloraz compound IB-107 one individualized Triflumizole compound I B-108 oneindividualized Benomyl compound I B-109 one individualized Carbendazimcompound I B-110 one individualized Fuberidazole compound I B-111 oneindividualized Thiabendazole compound I B-112 one individualizedEthaboxam compound I B-113 one individualized Etridiazole compound IB-114 one individualized Hymexazole compound I B-115 one individualized2-(4-Chloro-phenyl)-N-[4-(3,4-dimeth- compound Ioxy-phenyl)-isoxazol-5-yl]-2-prop-2-yn- yloxy-acetamide B-116 oneindividualized Fluazinam compound I B-117 one individualized Pyrifenoxcompound I B-118 one individualized3-[5-(4-Chloro-phenyl)-2,3-dimethyl-is- compound Ioxazolidin-3-yl]pyridine (Pyrisoxazole) B-119 one individualized3-[5-(4-Methyl-phenyl)-2,3-dimethyl- compound Iisoxazolidin-3-yl]-pyridine B-120 one individualized Bupirimate compoundI B-121 one individualized Cyprodinil compound I B-122 oneindividualized 5-Fluorocytosine compound I B-123 one individualized5-Fluoro-2-(p-tolylmethoxy)pyrimidin- compound I 4-amine B-124 oneindividualized 5-Fluoro-2-(4-fluorophenylmethoxy)- compound Ipyrimidin-4-amine B-125 one individualized Diflumetorim compound I B-126one individualized (5,8-Difluoroquinazolin-4-yl)-{2-[2- compound Ifluoro-4-(4-trifluoromethylpyridin-2- yloxy)-phenyl]-ethyl}-amine B-127one individualized Fenarimol compound I B-128 one individualizedFerimzone compound I B-129 one individualized Mepanipyrim compound IB-130 one individualized Nitrapyrin compound I B-131 one individualizedNuarimol compound I B-132 one individualized Pyrimethanil compound IB-133 one individualized Triforine compound I B-134 one individualizedFenpiclonil compound I B-135 one individualized Fludioxonil compound IB-136 one individualized Aldimorph compound I B-137 one individualizedDodemorph compound I B-138 one individualized Dodemorph-acetate compoundI B-139 one individualized Fenpropimorph compound I B-140 oneindividualized Tridemorph compound I B-141 one individualizedFenpropidin compound I B-142 one individualized Fluoroimid compound IB-143 one individualized Iprodione compound I B-144 one individualizedProcymidone compound I B-145 one individualized Vinclozolin compound IB-146 one individualized Famoxadone compound I B-147 one individualizedFenamidone compound I B-148 one individualized Flutianil compound IB-149 one individualized Octhilinone compound I B-150 one individualizedProbenazole compound I B-151 one individualized Fenpyrazamine compound IB-152 one individualized Acibenzolar-S-methyl compound I B-153 oneindividualized Ametoctradin compound I B-154 one individualizedAmisulbrom compound I B-155 one individualized[(3S,6S,7R,8R)-8-benzyl-3-[(3-isobuty- compound Iryloxymethoxy-4-methoxypyridine- 2-carbonyl)amino]-6-methyl-4,9-dioxo-[1,5]dioxonan-7-yl] 2-methylpropanoate B-156 one individualized[(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy- compound I4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2-methylpropanoate B-157 oneindividualized [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acet compound Ioxymethoxy)-4-methoxy-pyridine- 2-carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2-methylpropanoate B-158 one individualized[(3S,6S,7R,8R)-8-benzyl-3-[(3-isobut- compound Ioxycarbonyloxy-4-methoxy-pyridine- 2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2-methylpropanoate B-159 one individualized[(3S,6S,7R,8R)-8-benzyl-3-[[3-(1,3-ben- compound Izodioxol-5-ylmethoxy)-4-methoxy-pyri-dine-2-carbonyl]amino]-6-methyl-4,9-di- oxo-1,5-dioxonan-7-yl] 2-methyl-propanoate B-160 one individualized (3S,6S,7R,8R)-3-[[(3-hydroxy-4-meth-compound I oxy-2-pyridinyl)carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)- 1,5-dioxonan-7-yl2-methylpropanoate B-161 one individualized Anilazin compound I B-162one individualized Blasticidin-S compound I B-163 one individualizedCaptafol compound I B-164 one individualized Captan compound I B-165 oneindividualized Chinomethionat compound I B-166 one individualizedDazomet compound I B-167 one individualized Debacarb compound I B-168one individualized Diclomezine compound I B-169 one individualizedDifenzoquat, compound I B-170 one individualizedDifenzoquat-methylsulfate compound I B-171 one individualized Fenoxanilcompound I B-172 one individualized Folpet compound I B-173 oneindividualized Oxolinsaure compound I B-174 one individualized Piperalincompound I B-175 one individualized Proquinazid compound I B-176 oneindividualized Pyroquilon compound I B-177 one individualized Quinoxyfencompound I B-178 one individualized Triazoxid compound I B-179 oneindividualized Tricyclazole compound I B-180 one individualized2-Butoxy-6-iodo-3-propyl-chromen-4- compound I one B-181 oneindividualized 5-Chloro-1-(4,6-dimethoxy-pyrimidin-2- compound Iyl)-2-methyl-1H-benzoimidazole B-182 one individualized5-Chloro-7-(4-methyl-piperidin-1-yl)- compound I6-(2,4,6-trifluoro-phenyl)-[1,2,4]tri- azolo[1,5-a]pyrimidine B-183 oneindividualized Ferbam compound I B-184 one individualized Mancozebcompound I B-185 one individualized Maneb compound I B-186 oneindividualized Metam compound I B-187 one individualized Methasulphocarbcompound I B-188 one individualized Metiram compound I B-189 oneindividualized Propineb compound I B-190 one individualized Thiramcompound I B-191 one individualized Zineb compound I B-192 oneindividualized Ziram compound I B-193 one individualized Diethofencarbcompound I B-194 one individualized Benthiavalicarb compound I B-195 oneindividualized Iprovalicarb compound I B-196 one individualizedPropamocarb compound I B-197 one individualized Propamocarb hydrochloridcompound I B-198 one individualized Valifenalate compound I B-199 oneindividualized N-(1-(1-(4-cyanophenyl)ethanesulfon- compound Iyl)-but-2-yl) carbamic acid-(4-fluoro- phenyl) ester B-200 oneindividualized Dodine compound I B-201 one individualized Dodine freebase compound I B-202 one individualized Guazatine compound I B-203 oneindividualized Guazatine-acetate compound I B-204 one individualizedIminoctadine compound I B-205 one individualized Iminoctadine-triacetatecompound I B-206 one individualized Iminoctadine-tris(albesilate)compound I B-207 one individualized Kasugamycin compound I B-208 oneindividualized Kasugamycin-hydrochloride-hydrate compound I B-209 oneindividualized Polyoxine compound I B-210 one individualizedStreptomycin compound I B-211 one individualized Validamycin A compoundI B-212 one individualized Binapacryl compound I B-213 oneindividualized Dicloran compound I B-214 one individualized Dinobutoncompound I B-215 one individualized Dinocap compound I B-216 oneindividualized Nitrothal-isopropyl compound I B-217 one individualizedTecnazen compound I B-218 one individualized Fentin salts compound IB-219 one individualized Dithianon compound I B-220 one individualized2,6-dimethyl-1H,5H-[1,4]dithiino compound I [2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetraone B-221 one individualized Isoprothiolane compoundI B-222 one individualized Edifenphos compound I B-223 oneindividualized Fosetyl, Fosetyl-aluminium compound I B-224 oneindividualized Iprobenfos compound I B-225 one individualizedPhosphorous acid (H₃PO₃) and compound I derivatives B-226 oneindividualized Pyrazophos compound I B-227 one individualizedTolclofos-methyl compound I B-228 one individualized Chlorothalonilcompound I B-229 one individualized Dichlofluanid compound I B-230 oneindividualized Dichlorophen compound I B-231 one individualizedFlusulfamide compound I B-232 one individualized Hexachlorbenzenecompound I B-233 one individualized Pencycuron compound I B-234 oneindividualized Pentachlorophenol and salts compound I B-235 oneindividualized Phthalide compound I B-236 one individualized Quintozenecompound I B-237 one individualized Thiophanate Methyl compound I B-238one individualized Tolylfluanid compound I B-239 one individualizedN-(4-chloro-2-nitro-phenyl)-N-ethyl- compound I4-methyl-benzenesulfonamide B-240 one individualized Bordeaux mixturecompound I B-241 one individualized Copper acetate compound I B-242 oneindividualized Copper hydroxide compound I B-243 one individualizedCopper oxychloride compound I B-244 one individualized basic Coppersulfate compound I B-245 one individualized Sulfur compound I B-246 oneindividualized Biphenyl compound I B-247 one individualized Bronopolcompound I B-248 one individualized Cyflufenamid compound I B-249 oneindividualized Cymoxanil compound I B-250 one individualizedDiphenylamin compound I B-251 one individualized Metrafenone compound IB-252 one individualized Pyriofenone compound I B-253 one individualizedMildiomycin compound I B-254 one individualized Oxin-copper compound IB-255 one individualized Oxathiapiprolin compound I B-256 oneindividualized Prohexadione calcium compound I B-257 one individualizedSpiroxamine compound I B-258 one individualized Tebufloquin compound IB-259 one individualized Tolylfluanid compound I B-260 oneindividualized N-(Cyclopropylmethoxyimino-(6- compound Idifluoromethoxy-2,3-difluoro-phenyl)- methyl)-2-phenyl acetamide B-261one individualized N′-(4-(4-chloro-3-trifluoromethyl- compound Iphenoxy)-2,5-dimethyl-phenyl)-N-ethyl- N-methyl formamidine B-262 oneindividualized N′-(4-(4-fluoro-3-trifluoromethyl- compound Iphenoxy)-2,5-dimethyl-phenyl)-N-ethyl- N-methyl formamidine B-263 oneindividualized N′-(2-methyl-5-trifluoromethyl-4-(3-tri- compound Imethylsilanyl-propoxy)-phenyl)-N-ethyl- N-methyl formamidine B-264 oneindividualized N′-(5-difluoromethyl-2-methyl-4-(3-tri- compound Imethylsilanyl-propoxy)-phenyl)-N-ethyl- N-methyl formamidine B-265 oneindividualized Methoxy-acetic acid 6-tert-butyl-8- compound Ifluoro-2,3-dimethyl-quinolin-4-yl ester B-266 one individualizedBacillus subtilis NRRL No. B-21661 compound I B-267 one individualizedBacillus pumilus NRRL No. B-30087 compound I B-268 one individualizedUlocladium oudemansii compound I B-269 one individualized Carbarylcompound I B-270 one individualized Carbofuran compound I B-271 oneindividualized Carbosulfan compound I B-272 one individualizedMethomylthiodicarb compound I B-273 one individualized Bifenthrincompound I B-274 one individualized Cyfluthrin compound I B-275 oneindividualized Cypermethrin compound I B-276 one individualizedalpha-Cypermethrin compound I B-277 one individualized zeta-Cypermethrincompound I B-278 one individualized Deltamethrin compound I B-279 oneindividualized Esfenvalerate compound I B-280 one individualizedLambda-cyhalothrin compound I B-281 one individualized Permethrincompound I B-282 one individualized Tefluthrin compound I B-283 oneindividualized Diflubenzuron compound I B-284 one individualizedFlufenoxuron compound I B-285 one individualized Lufenuron compound IB-286 one individualized Teflubenzuron compound I B-287 oneindividualized Spirotetramate compound I B-288 one individualizedClothianidin compound I B-289 one individualized Dinotefuran compound IB-290 one individualized Imidacloprid compound I B-291 oneindividualized Thiamethoxam compound I B-292 one individualizedFlupyradifurone compound I B-293 one individualized Acetamiprid compoundI B-294 one individualized Thiacloprid compound I B-295 oneindividualized Endosulfan compound I B-296 one individualized Fipronilcompound I B-297 one individualized Abamectin compound I B-298 oneindividualized Emamectin compound I B-299 one individualized Spinosadcompound I B-300 one individualized Spinetoram compound I B-301 oneindividualized Hydramethylnon compound I B-302 one individualizedChlorfenapyr compound I B-303 one individualized Fenbutatin oxidecompound I B-304 one individualized Indoxacarb compound I B-305 oneindividualized Metaflumizone compound I B-306 one individualizedFlonicamid compound I B-307 one individualized Lubendiamide compound IB-308 one individualized Chlorantraniliprole compound I B-309 oneindividualized Cyazypyr (HGW86) compound I B-310 one individualizedCyflumetofen compound I B-311 one individualized Acetochlor compound IB-312 one individualized Dimethenamid compound I B-313 oneindividualized metolachlor compound I B-314 one individualizedMetazachlor compound I B-315 one individualized Glyphosate compound IB-316 one individualized Glufosinate compound I B-317 one individualizedSulfosate compound I B-318 one individualized Clodinafop compound IB-319 one individualized Fenoxaprop compound I B-320 one individualizedFluazifop compound I B-321 one individualized Haloxyfop compound I B-322one individualized Paraquat compound I B-323 one individualizedPhenmedipham compound I B-324 one individualized Clethodim compound IB-325 one individualized Cycloxydim compound I B-326 one individualizedProfoxydim compound I B-327 one individualized Sethoxydim compound IB-328 one individualized Tepraloxydim compound I B-329 oneindividualized Pendimethalin compound I B-330 one individualizedProdiamine compound I B-331 one individualized Trifluralin compound IB-332 one individualized Acifluorfen compound I B-333 one individualizedBromoxynil compound I B-334 one individualized Imazamethabenz compound IB-335 one individualized Imazamox compound I B-336 one individualizedImazapic compound I B-337 one individualized Imazapyr compound I B-338one individualized Imazaquin compound I B-339 one individualizedImazethapyr compound I B-340 one individualized2,4-Dichlorophenoxyacetic acid (2,4-D) compound I B-341 oneindividualized Chloridazon compound I B-342 one individualizedClopyralid compound I B-343 one individualized Fluroxypyr compound IB-344 one individualized Picloram compound I B-345 one individualizedPicolinafen compound I B-346 one individualized Bensulfuron compound IB-347 one individualized Chlorimuron-ethyl compound I B-348 oneindividualized Cyclosulfamuron compound I B-349 one individualizedIodosulfuron compound I B-350 one individualized Mesosulfuron compound IB-351 one individualized Metsulfuron-methyl compound I B-352 oneindividualized Nicosulfuron compound I B-353 one individualizedRimsulfuron compound I B-354 one individualized Triflusulfuron compoundI B-355 one individualized Atrazine compound I B-356 one individualizedHexazinone compound I B-357 one individualized Diuron compound I B-358one individualized Florasulam compound I B-359 one individualizedPyroxasulfone compound I B-360 one individualized Bentazone compound IB-361 one individualized Cinidon-ethyl compound I B-362 oneindividualized Cinmethylin compound I B-363 one individualized Dicambacompound I B-364 one individualized Diflufenzopyr compound I B-365 oneindividualized Quinclorac compound I B-366 one individualized Quinmeraccompound I B-367 one individualized Mesotrione compound I B-368 oneindividualized Saflufenacil compound I B-369 one individualizedTopramezone compound I

The active substances referred to as component 2, their preparation andtheir activity against harmful fungi is known (cf.:http://www.alanwood.net/pesticides/); these substances are commerciallyavailable. The compounds described by IUPAC nomenclature, theirpreparation and their fungicidal activity are also known (cf. Can. J.Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031; EP-A 226917; EP-A 243 970; EP-A 256 503; EP-A 428 941; EP-A 532 022; EP-A 1 028125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1 122 244, JP 2002316902; DE19650197; DE 10021412; DE 102005009458; U.S. Pat. No. 3,296,272; U.S.Pat. No. 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783;WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501; WO 01/56358; WO02/22583; WO 02/40431; WO 03/10149; WO 03/11853; WO 03/14103; WO03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491; WO04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO05/63721; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO06/87343; WO 07/82098; WO 07/90624, WO 11/028657).

The mixtures of active substances can be prepared as compositionscomprising besides the active ingredients at least one inert ingredientby usual means, e. g. by the means given for the compositions ofcompounds I.

Concerning usual ingredients of such compositions reference is made tothe explanations given for the compositions containing compounds I.

The mixtures of active substances according to the present invention aresuitable as fungicides, as are the compounds of formula I. They aredistinguished by an outstanding effectiveness against a broad spectrumof phytopathogenic fungi, especially from the classes of theAscomycetes, Basidiomycetes, Deuteromycetes and Peronosporomycetes (syn.Oomycetes). In addition, it is referred to the explanations regardingthe fungicidal activity of the compounds and the compositions containingcompounds I, respectively.

I. SYNTHESIS EXAMPLES

With due modification of the starting compounds, the procedures shown inthe synthesis examples below were used to obtain further compounds I.The resulting compounds, together with physical data, are listed inTable I below.

I.1 Preparation of Strobilurin Type Compounds I Example 1: Preparationof(Z)-5-[1-(4-Chloro-phenyl)-1H-pyrazol-3-yloxy]-2-[(E)-meth-oxyimino]-3-methyl-pent-3-enicacid methyl amide (I-6)

Ex. 1a: (Z)-3-Tributylstannanyl-but-2-en-1-ol (3)

To 156.9 ml (156.9 mmol) of a 1 molar solution oflithium-aluminum-hydride in THF 0.77 g (14.3 mmol) sodium methylate havebeen added and the temperature has been lowered to 0° C. afterwards.Then a solution of 10.0 g (142.7 mmol) 2-butin-1-ol in 108 ml THF hasbeen added dropwise with stirring at this temperature. Stirring wascontinued for 36 h at 4° C. Thereafter, at about 0° C., 28.6 ml (292.5mmol) ethyl acetate was-added slowly while stirring. A stronglyexothermic reaction was observed. Stirring was continued for 10 minwithout cooling. After cooling to about 0° C., 45.8 g (142.7 mmol)tri(n-butyl)stannyl-methanolate have been added dropwise while stirring.Stirring was continued for 2 d at 4° C. After addition of 112.9 gmethanol stirring was continued for 1 h at ambient temperature. Thereaction mixture was poured into 250 ml of water, extracted thrice with150 ml diethyl ether each, the combined extracts were washed twice with80 ml of water each, then once with 40 ml saturated aqueous sodiumchloride solution, dried with sodium sulfate and concentrated in vacuo.Yield 48.6 g oil, which have been purified by chromatography on 300 gsilica gel with hexane/MTBE (10:1). Final yield 34.6 g (67%) oil. δ=0.90(m); 1.30 (m); 1.50 m); 1.97 (s); 4.02 (t); 6.27 (t).

Ex. 1b:1-(4-Chloro-phenyl)-3-((Z)-3-tributylstannanyl-but-2-enyloxy)-1H-pyrazole(5)

To 8.09 g (30.8 mmol) triphenylphosphine in 200 ml THF have been addedwith stirring at −75° C. 6.23 g (30.8 mmol) azodicarbonic aciddiisopropyl ester. The mixture has been stirred at this temperature for5 min. Then 10.39 g (28.8 mmol) (Z)-3-tributylstannanyl-but-2-en-1-olhave been added dropwise and stirred for 5 min at −75° C. After additionof 4.00 g (20.6 mmol) 1-(4-chlorophenyl)-3-hydroxypyrazole at −75° C. ared suspension was formed. The mixture was allowed to warm up to ambienttemperature and stirred for 3 d. After removal of the solvents in vacuo29 g oil have been collected and purified by chromatography on 120 gsilica with MTBE/heptane. Yield 8.3 g (75%) oil. δ=0.85 (m); 0.95 (m);1.30 (m); 1.50 m); 2.00 (s); 4.65 (d); 5.90 (d); 6.43 (t); 7.35 (d);7.52 (d); 7.68 (d).

Ex. 1c:(Z)-5-[1-(4-Chloro-phenyl)-1H-pyrazol-3-yloxy]-2-[(E)-methoxyimino]-3-methyl-pent-3-enicacid methyl ester (7)

3.00 g (5.58 mmol)1-(4-Chloro-phenyl)-3-((Z)-3-tributylstannanyl-but-2-enyloxy)-1H-pyrazole,1.15 g (5.86 mmol) hydroxamic acid bromide (6), 0.155 g (0.67 mmol)tri(2-furyl)phosphine and 96 mg (0.17 mmol)bis(dibenzylidenacetone)-palladium have been stirred in 10 ml1,4-dioxane for 4 d at about 80° C. After removal of the solvents invacuo 4.3 g oil have been collected and purified by chromatography on 70g silica with MTBE/heptane/1% triethylamine. Yield 1.2 g (59%) oil.δ=1.95 (s); 3.85 (s); 4.07 (s); 4.58 (d); 5.85 (d); 5.93 (t); 7.35 (d);7.52 (d); 7.65 (d).

Ex. 1d:(Z)-5-[1-(4-Chloro-phenyl)-1H-pyrazol-3-yloxy]-2-[(E)-methoxyimino]-3-methyl-pent-3-enicacid methyl amide (I-6)

120 mg (0.33 mmol)(Z)-5-[1-(4-chloro-phenyl)-1H-pyrazol-3-yloxy]-2-[(E)-methoxyimino]-3-methyl-pent-3-enicacid methyl ester and 0.99 ml (1.98 mmol) of a 2-molar solution ofmethyl amine in THF have been stirred overnight at ambient temperaturein 2.0 ml of THF and 0.5 ml of water. After removal of the solvent invacuo the product (120 mg) was collected in quantitative yield and goodpurity. Melting point 129-130° C.

Example 2:(Z)-5-[1-(4-Chloro-phenyl)-1H-pyrazol-3-yloxy]-2-[1-methoxy-meth-(E)-yl-idene]-3-methyl-pent-3-enoicacid methyl ester (compound I-7)

1.50 g (2.79 mmol)1-(4-Chloro-phenyl)-3-((Z)-3-tributylstannanyl-but-2-enyloxy)-1H-pyrazole(5), 0.81 g (3.35 mmol) of ester compound (8) [Chem Comm 4, 423-425,(2006)], 0.223 g (0.28 mmol)[(R)-(+)-2,2″-Bis(diphenylphosphino)-1,1″-bisnaphthyl]-palladium(II)chloridehave been stirred in 14 ml 1,4-dioxane for 4.5 d at about 100° C. Afterremoval of the solvents in vacuo the crude product has been collected,which has been purified by chromatography on 50 g silica withMTBE/hexane/2% triethylamine. Yield 0.12 g, melting point 123-125° C.

Example 3: MethylN—[(Z)-3-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-1-methyl-prop-1-enyl]-N-methyl-carbamate(I-10)

Ex. 3a: 1-(4-chlorophenyl)-3-[(Z)-3-iodobut-2-enoxy]pyrazole (10)

To 10.0 g (18.6 mmol)1-(4-chloro-phenyl)-3-((Z)-3-tributylstannanyl-but-2-enyloxy)-1H-pyrazolein 100 ml methylene chloride have been added 4.7 g (18.6 mmol) iodine atambient temperature with stirring which was continued for 3 h. Afterremoval of the solvents in vacuo the crude product was dissolved in 200ml MTBE. 100 ml 20% aqueous potassium fluoride solution have been addedand the mixture was stirred for 2 h at ambient temperature. The aqueouslayer was separated and extracted with 20 ml methyl-tert.-butyl ethertwice. The combined organic phases have been washed twice with 20 ml ofwater each, dried with sodium sulfate, and the solvents were removed invacuo. The crude product (7.2 g) has been purified by chromatography on50 g silica with methyl-tert.-butylether/hexane (1:20). Yield 5.9 g,melting point 75-77° C.

Ex. 3b: MethylN—[(Z)-3-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-1-methyl-prop-1-enyl]-N-methyl-carbamate

1.50 g (4.00 mmol) 1-(4-chlorophenyl)-3-[(Z)-3-iodobut-2-enoxy]pyrazole,0.43 g (4.81 mmol) N-methylcarbamic acid methyl ester (9), 76 mg (0.4mmol) copperiodide, 1.27 g (6.00 mmol) potassium phosphate and 71 mg(0.80 mmol) N,N′-dimethylethylene diamine in 14 ml toluene have beenstirred for 1.5 d at 100° C. After removal of the solvents in vacuo thecrude product has been purified by chromatography on 50 g silica withMTBE/hexane (1:3). Yield 0.67 g. ¹H-NMR (CDCl₃): δ=1.90 (s); 3.05 (s);3.70 (s); 4.68 (m); 5.63 (m); 5.90 (d); 7.35 (m); 7.55 (m); 7.68 (d).

Example 4:(Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,4-dimethyl-pent-3-enamide(compound I-79)

Ex. 4a: 1-[1-(4-Chlorophenyl)pyrazol-3-yl]oxypropan-2-one (11)

5.50 g (28.3 mmol) 1-(4-chlorophenyl)pyrazol-3-ol, 3.91 g (28.3 mmol)potassium carbonate and 50 mg sodium iodide in 30 ml DMF have beenstirred for 5 min at ambient temperature. Then 2.62 g (28.3 mmol)chloroacetone have been added dropwise while stirring which wascontinued at 60° C. for 5 h. The mixture was poured into excess 10%aqueous lithium chloride solution and extracted with ethyl acetate threetimes. The combined extracts have been washed with 10% lithium chloridesolution twice and dried with sodium sulfate. After removal of thesolvent in vacuo the crude product has been purified by chromatographyon silica. Yield 6.5 g. The product was used for the next step.

Ex. 4b: Methyl(Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-4-methyl-pent-3-enoateand E-isomer (13)

To 5.26 g (21.0 mmol) 1-[1-(4-chlorophenyl)pyrazol-3-yl]oxypropan-2-oneand 7.20 g (26.9 mmol) methyl(2Z)-3-diethoxyphosphoryl-2-methoxyimino-propanoate (which can beprepared as described for the dimethoxy derivative [(Tetrahedron Let 29,3361-3364 (1988)] in 100 ml THF have been added at ambient temperaturewith stirring 2.59 g (23.1 mmol) potassium tert.-butylate. Stirring wascontinued over night. After removal of the solvent in vacuo the mixturewas purified by chromatography on silica with heptane/ethyl acetate.1.07 g of a 80:20 E:Z-mixture have been collected. This has been useddirectly for the next step.

Ex. 4c:Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,4-dimethyl-pent-3-enamide

0.68 g (1.87 mmol) methyl(Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-4-methyl-pent-3-enoateand E-isomer from the previous reaction have been dissolved in 3.0 mlTHF. 2.0 ml 40% aqueous methylamine have been added at ambienttemperature with stirring which was continued over night. After removalof the solvent in vacuo the mixture was purified by chromatography onsilica with a heptane/ethyl acetate gradient. 90 mg of the desiredZ-isomer have been collected. ¹H-NMR (CDCl₃): δ=2.03 (s); 2.85 (d); 3.97(s); 4.64 (s); 5.87 (s); 6.02 (d); 6.65 (br); 7.35 (d); 7.50 (d); 7.67(d).

Example 5: MethylN—[(Z)-3-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-1-methyl-prop-1-enyl]-N-methoxy-carbamate(I-1)

Ex. 5a: Cis-3-methyloxiran-2-yl]methanol (15)

To 10.0 g (138.7 mmol) Z-but-2-en-1-ol in 140 ml dichloromethane (DCM)37.6 g (152.6 mmol) 3-chloroperbenzoic acid (70% purity) have been addedat 0-5° C. in small portions with stirring. Stirring was continued at 0°C. for 2 h. 35.0 g calcium hydroxide have been added at 0-5° C. withstirring which was continued for about 2 h at 0° C. The precipitate wasfiltered off, washed with DCM, and the filtrates dried with sodiumsulfate. The solvent was largely removed at 380 mbar/30° C. The crudeproduct (15.0 g, purity 75%) was used without further purification.

Ex. 5b: Racemic1-(4-chlorophenyl)-3-[[(2R,3S)-3-methyloxiran-2-yl]methoxy]pyrazole (16)

To 28.3 g (107.9 mmol) triphenylphosphine and 15.0 g (127.7 mmol)cis-3-methyloxiran-2-yl]methanol (15) from the preceding experiment in400 ml THF have been added with stirring at −75° C. 22.9 g (113.0 mmol)azodicarbonic acid diisopropyl ester. The mixture has been stirred atthis temperature for 5 min. Then 20.0 g (102.8 mmol)1-(4-chlorophenyl)-3-hydroxypyrazole have been added with stirring at−70° C. The mixture was allowed to warm up to ambient temperature andstirred for about 1 d. After removal of the solvents in vacuo the crudeproduct was stirred with 200 ml of diisopropylether from which 42 g of asolid substance have been collected and further purified bychromatography on 330 g silica with MTBE/heptane. Yield 22.5 g (82%).

Ex. 5c:5-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methoxy-4-methyl-oxazolidin-2-one(17)

To 1.08 g (10.0 mmol) methyl N-methoxycarbamate in 17 ml DMSO have beenadded with stirring at ambient temperature 1.00 g (8.9 mmol) potassiumtert.-butylate. Stirring has been continued for 5 min before 2.00 g(7.56 mmol)1-(4-chlorophenyl)-3-[[(2R,3S)-3-methyloxiran-2-yl]methoxy]pyrazole havebeen added. The mixture was stirred at 90° C. for 20 h. After cooling toambient temperature the reaction mixture was poured into 150 ml ofwater, extracted thrice with 30 ml ethyl acetate each, the combinedextracts have been dried with sodium sulfate and the solvent removed invacuo. The crude product (2.5 g) was used without further purification.

Ex. 5d: Racemic(2S,3R-1-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-3-(methoxyamino)butan-2-ol(18)

To 10.0 g (30.0 mmol)5-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methoxy-4-methyl-oxazolidin-2-onein 100 ml ethanol has been added at ambient temperature with stirring14.6 g (40.0 mmol) 21% sodium ethylate solution (in ethanol) and stirredover night. The solvent was largely removed in vacuo and the remainingmixture poured into 250 ml aqueous sodium dihydrogenphosphate solution,extracted thrice with 150 ml ethyl acetate each, dried with sodiumsulfate to yield 8.7 g of an oil after evaporation of the solvent invacuo. Further purified by chromatography on 120 g silica withMTBE/heptane. Yield 4.0 g (43%). ¹H-NMR (CDCl₃): δ=1.22 (d); 3.17 (m);3.57 (s); 3.91 (m); 4.33 (m); 4.47 (m); 5.93 (s); 7.35 (d); 7.52 (d);7.68 (s).

Ex. 5e: Racemic methylN-[(1R,2S)-3-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-hydroxy-1-methyl-propyl]-N-methoxy-carbamate(19)

To 1.00 g (3.2 mmol) Racemic(2S,3R-1-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-3-(methoxyamino)butan-2-olin 7 ml THF 0.28 g (3.5 mmol) sodium hydrogencarbonate has been added.Then 0.33 g (3.5 mmol) methyl chloroformiate has been added dropwisewith stirring at ambient temperature. Stirring has been continued overnight. The reaction mixture was poured into 10 ml of water, extractedthrice with 10 ml MTBE each, the combined extracts dried with sodiumsulfate, and the solvent removed in vacuo. The crude product (1.3 g) wasused without further purification.

Ex. 5f: MethylN—[(Z)-3-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-1-methyl-prop-1-enyl]-N-methoxy-carbamate(I-1)

To 3.50 g (9.46 mmol) racemic methylN-[(1R,2S)-3-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-hydroxy-1-methyl-propyl]-N-methoxy-carbamatein 13 ml THF 2.61 g (9.94 mmol) triphenylphoshin has been added withstirring at ambient temperature. The mixture was cooled to −15° C. Then2.11 g (10.41 mmol) azodicarbonic acid diisopropyl ester has been addedwith stirring which was continued for 1 h at 0° C. and for about 1 d atambient temperature. After removal of the solvents in vacuo the crudeproduct was further purified by chromatography on 25 g silica withMTBE/heptane/1% triethylamine. ¹H-NMR (CDCl₃): δ=1.93 (s); 3.72 (s);3.81 (s); 4.78 (d); 5.73 (t); 5.90 (d); 7.36 (d); 7.55 (d); 7.70 (d).

TABLE I Compounds of formula I with physical data (melting point [° C.];¹H-NMR (CDCl₃) (δ); HPLC/MS retention time [min]) No. R¹ R² R³ R⁴ X Ym.p. [° C.]; ¹H-NMR (δ); R_(t) [min] I-1 CH₃ H R3-1 R4-4, O Y-1 δ = 1.93(s); 3.72 (s); 3.81 (s); R⁵═OCH₃ 4.78 (d); 5.73 (t); 5.90 (d); 7.36 (d);7.55 (d); 7.70 (d) I-2 CH₃ H R3-1 R4-4, NH Y-1 R⁵═OCH₃ I-3 CH₃ H R3-1R4-3 O Y-1 I-4 CH₃ H R3-1 R4-3 NH Y-1 I-5 CH₃ H R3-1 R4-1 O Y-1  88-89°C. I-6 CH₃ H R3-1 R4-1 NH Y-1 130° C. I-7 CH₃ H R3-1 R4-2 O Y-1 123-125°C. I-8 CH₃ H R3-1 R4-2 NH Y-1 I-9 CH₃ H R3-1 R4-7 Y-1 I-10 CH₃ H R3-1R4-4, O Y-1 δ = 1.90 (s); 3.05 (s); 3.70 (s); R⁵═OCH₃ 4.68 (m); 5.63(m); 5.90 (d); 7.35 (m); 7.55 (m); 7.68 (d) I-11 CH₃ H R3-2 R4-1 NH Y-1δ = 1.95 (s); 2.85 (d); 3.95 (s); 4.55 (m); 5.87 (m); 5.95 (m); 6.70(br); 6.95 (m); 7.73 (m); 7.80 (m) I-12 CH₃ H R3-3 R4-1 NH Y-1 δ = 1.95(s); 2.27 (s); 2.80 (d); 3.95 (s); 4.52 (m); 5.83 (d); 5.93 (m); 6.75(br); 6.95 (m); 7.30 (m) I-13 CH₃ H R3-4 R4-1 NH Y-1 δ = 1.93 (s); 2.38(s); 2.80 (d); 3.95 (s); 4.55 (m); 5.88 (d); 5.95 (m); 6.75 (br); 7.13(m); 7.28 (m); 7.41 (d); 7.64 (d) I-14 CH₃ H R3-5 R4-1 NH Y-1 125-127°C. I-15 CH₃ H R3-6 R4-1 NH Y-1 δ = 1.95 (s); 2.85 (d); 3.95 (s); 4.55(m); 5.90 (d); 5.95 (m); 6.70 (br); 7.32 (m); 7.50 (s); 7.54 (d); 7.70(d) I-16 CH₃ H R3-7 R4-1 NH Y-1 δ = 1.95 (s); 2.90 (d); 3.97 (s); 4.56(m); 5.88 (d); 5.94 (m); 6.70 (br); 7.45 (m); 7.64 (s); 7.72 (d) I-17CH₃ H R3-8 R4-1 NH Y-1 I-18 CH₃ H R3-9 R4-1 NH Y-1 δ = 1.95 (s); 2.33(s); 2.88 (d); 3.97 (s); 4.56 (m); 5.85 (m); 5.95 (m); 6.70 (br); 7.03(t); 7.30 (m); 7.44 (m); 7.62 (m) I-19 CH₃ H R3-10 R4-1 NH Y-1 I-20 CH₃H R3-11 R4-1 NH Y-1 δ = 1.95 (s); 2.25 (s); 2.30 (s); 2.87 (d); 3.97(s); 4.56 (m); 5.85 (d); 5.95 (m); 6.73 (br); 7.15 (d); 7.27 (m); 7.35(d); 7.63 (d) I-21 CH₃ H R3-12 R4-1 NH Y-1 I-22 CH₃ H R3-13 R4-1 NH Y-1I-23 CH₃ H R3-14 R4-1 NH Y-1 I-24 CH₃ H R3-15 R4-1 NH Y-1 I-25 CH₃ HR3-16 R4-1 NH Y-1 I-26 CH₃ H R3-17 R4-1 NH Y-1 I-27 CH₃ H R3-14 R4-1 NHY-1 I-28 CH₃ H R3-18 R4-1 NH Y-1 δ = 1.95 (s); 2.90 (d); 3.97 (s); 4.57(m); 5.87 (m); 5.95 (m); 6.70 (br); 7.07 (m); 7.33 (m); 7.55 (m); 7.64(m) I-29 CH₃ H R3-19 R4-1 NH Y-1 δ = 1.95 (s); 2.90 (d); 3.97 (s); 4.58(m); 5.88 (d); 5.94 (m); 6.70 (br); 7.15 (m); 7.30 (m); 7.43 (m); 7.64(s); 7.70 (d) I-30 CH₃ H R3-20 R4-1 NH Y-1 I-31 CH₃ H R3-21 R4-1 NH Y-1I-32 CH₃ H R3-22 R4-1 NH Y-1 δ = 1.95 (s); 2.37 (s); 2.87 (d); 3.95 (s);4.55 (m); 5.86 (d); 5.93 (m); 6.70 (br); 7.20 (m); 7.45 (m); 7.65 (d)I-33 CH₃ H R3-23 R4-1 NH Y-1 δ = 1.23 (m); 1.95 (s); 2.64 (m); 2.87 (d);3.95 (s); 4.58 (m); 5.87 (d); 5.95 (m); 6.70 (br); 7.25 (m); 7.48 (m);7.67 (d) I-34 CH₃ H R3-24 R4-1 NH Y-1 δ = 1.95 (s); 2.90 (d); 3.97 (s);4.58 (m); 5.92 (m); 6.70 (br); 7.67 (m); 7.75 (d) I-35 CH₃ H R3-25 R4-1NH Y-1 I-36 CH₃ H R3-26 R4-1 NH Y-1 I-37 CH₃ H R3-58 R4-1 NH Y-1 I-38CH₃ H R3-28 R4-1 NH Y-1 I-39 CH₃ H R3-29 R4-1 NH Y-1 I-40 CH₃ H R3-30R4-1 NH Y-1 I-41 CH₃ H R3-31 R4-1 NH Y-1 I-42 CH₃ H R3-32 R4-1 NH Y-1I-43 CH₃ H R3-33 R4-1 NH Y-1 I-44 CH₃ H R3-34 R4-1 NH Y-1 I-45 CH₃ HR3-35 R4-1 NH Y-1 I-46 CH₃ H R3-36 R4-1 NH Y-1 I-47 CH₃ H R3-37 R4-1 NHY-1 I-48 CH₃ H R3-38 R4-1 NH Y-1 I-49 CH₃ H R3-39 R4-1 NH Y-1 I-50 CH₃ HR3-40 R4-1 NH Y-1 I-51 CH₃ H R3-41 R4-1 NH Y-1 I-52 CH₃ H R3-42 R4-1 NHY-1 I-53 CH₃ H R3-43 R4-1 NH Y-1 I-54 CH₃ H R3-44 R4-1 NH Y-1 I-55 CH₃ HR3-45 R4-1 NH Y-1 I-56 CH₃ H R3-46 R4-1 NH Y-1 I-57 CH₃ H R3-47 R4-1 NHY-1 I-58 CH₃ H R3-45 R4-1 NH Y-1 I-59 CH₃ H R3-49 R4-1 NH Y-1 I-60 CH₃ HR3-50 R4-1 NH Y-1 I-61 CH₃ H R3-51 R4-1 NH Y-1 I-62 CH₃ H R3-52 R4-1 NHY-1 I-63 CH₃ H R3-53 R4-1 NH Y-1 I-64 CH₃ H R3-54 R4-1 NH Y-1 I-65 CH₃ HR3-55 R4-1 NH Y-1 I-66 CH₃ H R3-56 R4-1 NH Y-1 I-67 CH₃ H R3-57 R4-1 NHY-1 I-68 CH₃ H R3-58 R4-4, O Y-1 R⁵═OCH₃ I-69 CH₃ H R3-58 R4-4, NH Y-1R⁵═OCH₃ I-70 CH₃ H R3-58 R4-3 O Y-1 I-71 CH₃ H R3-58 R4-3 NH Y-1 I-72CH₃ H R3-27 R4-1 O Y-1 I-73 CH₃ H R3-58 R4-2 O Y-1 I-74 CH₃ H R3-58 R4-2NH Y-1 I-75 CH₃ H R3-58 R4-7 Y-1 I-76 C₂H₅ H R3-1 R4-1 NH Y-1 I-77 C2H₅H R3-2 R4-1 NH Y-1 I-78 C2H₅ H R3-58 R4-1 NH Y-1 I-79 H CH₃ R3-1 R4-1 NHY-1 δ = 2.03 (s); 2.85 (d); 3.97 (s); 4.64 (s); 5.87 (s); 6.02 (d); 6.65(br); 7.35 (d); 7.50 (d); 7.67 (d) I-80 H CH₃ R3-1 R4-1 O Y-1 I-81 CH₃ HR3-1 R4-1 NH Y-3 I-82 CH₃ H R3-59 R4-1 NH Y-1 δ = 1.95 (s); 2.16 (s);2.18 (s); 2.30 (s); 2.90 (s); 3.97 (s); 4.33 (m); 4.65 (m); 5.30 (m);5.87 (m); 6.07 (m); 6.55 (s); 6.65 (br); 6.96 (s) I-83 CH₃ H R3-60 R4-1NH Y-1 δ = 1.95 (s); 2.22 (s); 2.90 (d); 3.95 (s); 4.35 (m); 4.67 (m);5.30 (m); 5.88 (m); 6.07 (m); 6.65 (br); 6.73 (d); 7.35 (d); 7.43 (s)I-84 CH₃ H R3-61 R4-1 NH Y-1 δ = 1.95 (s); 2.15 (s); 2.18 (s); 2.28 (s);2.90 (d); 3.95 (s); 4.33 (m); 4.67 (s); 5.39 (d); 5.43 (d); 5.88 (m);6.57 (s); 6.65 (br); 6.95 (s) I-85 CH₃ H R3-62 R4-1 NH Y-1 δ = 1.95 (s);2.21 (s); 2.25 (s); 2.89 (d); 3.95 (s); 4.35 (m); 4.70 (s); 5.39 (d);5.44 (d); 5.90 (m); 6.65 (br); 6.73 (d); 7.40 (d); 7.45 (s) I-86 CH₃ HR3-63 R4-1 O Y-1 δ = 1.73 (m); 1.93 (s); 2.15 (s); 2.30 (s); 3.85 (s);4.05 (s); 4.33 (m); 4.60 (m); 5.75 (m); 5.85 (m); 6.55 (s); 6.95 (s)I-87 CH₃ H R3-64 R4-1 O Y-1 δ = 1.95 (s); 2.12 (s); 2.14 (s); 2.30 (s);3.85 (s); 4.07 (s); 4.35 (m); 4.63 (m); 5.85 (m); 6.15 (m); 6.27 (m);6.55 (s); 6.97 (s) I-88 CH₃ H R3-65 R4-1 0 Y-1 δ = 1.95 (s); 2.17 (s);2.19 (s); 3.85 (s); 4.05 (s); 4.35 (m); 4.65 (m); 5.87 (m); 6.17 (m);6.31 (m); 6.72 (d); 7.35 (d); 7.43 (s). I-89 CH₃ H R3-66 R4-1 NH Y-1 δ =1.95 (s); 2.12 (s); 2.14 (s); 2.30 (s); 2.90 (d); 3.95 (s); 3.97 (s);4.32 (m); 5.87 (m); 6.57 (s); 6.65 (br); 6.97 (s) I-90 CH₃ H R3-63 R4-1NH Y-1 δ = 1.73 (m); 1.93 (s); 2.15 (s); 2.30 (s); 2.90 (d); 3.95 (s);4.33 (m); 4.55 (m); 5.75 (m); 5.90 (m); 6.57 (s); 6.65 (br); 6.95 (s)I-91 CH₃ H R3-67 R4-1 NH Y-1 δ = 1.73 (m); 1.93 (s); 2.18 (s); 2.20 (s);2.90 (d); 3.95 (s); 4.35 (m); 4.60 (m); 5.75 (m); 5.90 (m); 6.55 (br);6.73 (m); 7.35 (m); 7.43 (s) I-92 CH₃ H R3-64 R4-1 NH Y-1 δ = 1.95 (s);2.15 (s); 2.30 (s); 2.90 (d); 3.95 (s); 4.33 (m); 4.60 (m); 5.87 (m);6.15 (m); 6.27 (m); 6.57 (s); 6.65 (br); 6.95 (s) I-93 CH₃ H R3-65 R4-1NH Y-1 δ = 1.95 (s); 2.19 (s); 2.21 (s); 2.90 (d); 3.95 (s); 4.35 (m);4.65 (m); 5.90 (m); 6.17 (m); 6.31 (m); 6.65 (br); 6.75 (d); 7.35 (m);7.43 (s) I-94 CH₃ H R3-59 R4-1 O Y-1 δ = 1.95 (s); 2.15 (s); 2.30 (s);3.85 (s); 4.07 (s); 4.33 (m); 4.63 (m); 5.30 (m); 5.87 (m); 6.07 (m);6.53 (s); 6.97 (s) I-95 CH₃ H R3-60 R4-1 O Y-1 δ = 1.93 (s); 2.22 (s);3.85 (s); 4.07 (s); 4.37 (m); 4.67 (m); 5.30 (m); 5.87 (m); 6.07 (m);6.70 (d); 7.37 (m); 7.45 (s) I-96 CH₃ H R3-61 R4-1 O Y-1 δ = 1.95 (s);2.15 (s); 2.17 (s); 2.28 (s); 3.87 (s); 4.07 (s); 4.33 (m); 4.67 (s);5.40 (d); 5.43 (d); 5.87 (m); 6.53 (s); 6.95 (s) I-97 CH₃ H R3-62 R4-1 OY-1 δ = 1.95 (s); 2.21 (s); 2.23 (s); 3.85 (s); 4.05 (s); 4.37 (m); 4.70(s); 5.39 (d); 5.42 (d); 5.87 (m); 6.70 (d); 7.38 (m); 7.45 (s) I-98 CH₃H R3-68 R4-1 O Y-1 δ = 1.23 (t); 1.87 (s); 2.08 (s); 2.27 (s); 3.70 (s);3.95 (s); 4.10 (q); 4.30 (m); 5.90 (m); 6.65 (s); 7.00 (s) I-99 CH₃ HR3-69 R4-1 O Y-1 I-100 CH₃ H R3-69 R4-1 NH Y-1 I-101 CH₃ H R3-69 R4-4, OY-1 R⁵═OCH₃ I-102 CH₃ H R3-70 R4-1 O Y-6 I-103 CH₃ H R3-70 R4-1 NH Y-6I-104 CH₃ H R3-70 R4-4, O Y-6 R⁵═OCH₃ I-105 CH₃ H R3-71 R4-1 0 Y-4 I-106CH₃ H R3-71 R4-1 NH Y-4 I-107 CH₃ H R3-71 R4-4, 0 Y-4 R⁵═OCH₃ I-108 CH₃H R3-72 R4-1 NH Y-1 I-109 CH₃ H R3-72 R4-1 O Y-1 I-110 CH₃ H R3-72 R4-4,O Y-1 R⁵═OCH₃ I-111 CH₃ H R3-72 R4-1 NH Y-2 I-112 CH₃ H R3-72 R4-1 O Y-2I-113 CH₃ H R3-72 R4-4, O Y-2 R⁵═OCH₃ I-114 CH₃ H R3-1 R4-4, O Y-2R⁵═OCH₃ I-115 CH₃ H R3-1 R4-4, NH Y-2 R⁵═OCH₃ I-116 CH₃ H R3-1 R4-3 OY-2 I-117 CH₃ H R3-1 R4-3 NH Y-2 I-118 CH₃ H R3-1 R4-1 O Y-2 I-119 CH₃ HR3-1 R4-1 NH Y-2 I-120 CH₃ H R3-1 R4-2 O Y-2 I-121 CH₃ H R3-1 R4-2 NHY-2 I-122 CH₃ H R3-1 R4-7 Y-2 I-123 CH₃ H R3-1 R4-4, O Y-2 R⁵═CH₃ I-124CH₃ H R3-73 R4-1 NH Y-1 I-125 CH₃ H R3-74 R4-1 NH Y-1 I-126 CH₃ H R3-75R4-1 NH Y-1 I-127 CH₃ H R3-76 R4-1 NH Y-1 I-128 CH₃ H R3-77 R4-1 NH Y-1I-129 CH₃ H R3-78 R4-1 NH Y-1 I-130 CH₃ H R3-78 R4-1 NH Y-1 I-131 CH₃ HR3-80 R4-1 NH Y-1 I-132 CH₃ H R3-81 R4-1 NH Y-1 I-133 CH₃ H R3-82 R4-1NH Y-1 I-134 CH₃ H R3-83 R4-1 NH Y-1 I-135 CH₃ H R3-84 R4-1 NH Y-1 I-136CH₃ H R3-85 R4-1 NH Y-1 I-137 CH₃ H R3-86 R4-1 NH Y-1 I-138 CH₃ H R3-87R4-1 NH Y-1 I-139 CH₃ H R3-88 R4-1 NH Y-1 I-140 CH₃ H R3-89 R4-1 NH Y-1I-141 CH₃ H R3-90 R4-1 NH Y-1 I-142 CH₃ H R3-91 R4-1 NH Y-1 I-143 CH₃ HR3-92 R4-1 NH Y-1 I-144 CH₃ H R3-93 R4-1 NH Y-1 I-145 CH₃ H R3-94 R4-1NH Y-1 I-146 CH₃ H R3-95 R4-1 NH Y-1 I-147 CH₃ H R3-96 R4-1 NH Y-1 I-148CH₃ H R3-97 R4-1 NH Y-1 I-149 CH₃ H R3-98 R4-1 NH Y-1 I-150 CH₃ H R3-99R4-1 NH Y-1 I-151 CH₃ H R3-100 R4-1 NH Y-1 I-152 CH₃ H R3-101 R4-1 NHY-1 I-153 CH₃ H R3-102 R4-1 NH Y-1 I-154 CH₃ H R3-103 R4-1 NH Y-1 I-155CH₃ H R3-104 R4-1 NH Y-1 I-156 CH₃ H R3-105 R4-1 NH Y-1 I-157 CH₃ HR3-106 R4-1 NH Y-1 I-158 CH₃ H R3-107 R4-1 NH Y-1 I-159 CH₃ H R3-108R4-1 NH Y-1 I-160 CH₃ H R3-109 R4-1 NH Y-1 I-161 CH₃ H R3-110 R4-1 NHY-1 I-162 CH₃ H R3-111 R4-1 NH Y-1 I-163 CH₃ H R3-112 R4-1 NH Y-1 I-164CH₃ H R3-113 R4-1 NH Y-1 I-165 CH₃ H R3-114 R4-1 NH Y-1 I-166 CH₃ HR3-115 R4-1 NH Y-1 I-167 CH₃ H R3-116 R4-1 NH Y-1 I-168 CH₃ H R3-117R4-1 NH Y-1 I-169 CH₃ H R3-118 R4-1 NH Y-4 I-170 CH₃ H RS-HQ R4-1 NH Y-4I-171 CH₃ H R3-120 R4-1 NH Y-4 I-172 CH₃ H R3-121 R4-1 NH Y-4 I-173 CH₃H R3-122 R4-1 NH Y-4 I-174 CH₃ H R3-123 R4-1 NH Y-4 I-175 CH₃ H R3-124R4-1 NH Y-4 I-176 CH₃ H R3-125 R4-1 NH Y-4 I-177 CH₃ H R3-126 R4-1 NHY-1 I-178 CH₃ OCH₃ R3-1 R4-4, O Y-1 R⁵═OCH₃ I-179 CH₃ OCH₃ R3-1 R4-4, OY-1 R⁵═OCH₃ I-180 CH₃ OCH₃ R3-1 R4-4, O Y-1 R⁵═OCH₃ I-181 CH₃ H R3-1R4-4, O Y-1 R⁵═OCH₃ I-182 CH₃ H R3-1 R4-1 NH Y-1 I-183 CH₃ H R3-1 R4-1 OY-1 I-184 CH₃ H R3-1 R4-2 NH Y-1 I-185 CH₃ H R3-1 R4-2 O Y-1 I-186 CH₃ HR3-127 R4-1 O Y-1  79-81° C. I-187 CH₃ H R3-127 R4-1 NH Y-1 δ = 1.95(s); 2.12 (s); 2.18 (s); 2.87 (d); 3.97 (s); 3.98 (s); 4.35 (m); 5.90(m); 6.65 (br); 7.35 (d); 7.43 (s) I-188 C₂H₅ H R3-1 R4-1 O Y-1 δ = 1.05(m); 2.30 (m); 3.85 (s); 4.05 (s); 4.62 (m); 5.90 (m); 7.35 (m); 7.52(m): 7.70 (d) I-189 CH₃ H R3-127 R4-4, O Y-1 δ = 1.90 (s); 2.22 (s);2.24 (s); R⁵═CH₃ 3.02 (s); 3.70 (s); 3.98 (s); 4.48 (m); 5.57 (m); 6.75(m); 7.40 (m); 7.45 (s) I-190 CH₃ H R3-66 R4-1 O Y-1 δ = 1.95 (s); 2.10(s); 2.13 (s); 2.30 (s); 3.85 (s); 3.92 (s); 4.05 (s); 4.35 (m); 5.87(m); 6.53 (s); 6.97 (s) I-191 CH₃ H R3-128 R4-1 O Y-1 δ= 1.30 (t); 1.95(s); 2.20 (s); 2.22 (s); 3.85 (s); 4.06 (s); 4.20 (q); 4.37 (m); 5.87(m); 6.71 (d); 7.37 (m); 7.45 (s) I-192 CH₃ H R3-128 R4-1 NH Y-1 δ =1.30 (1); 1.95 (s); 2.20 (s); 2.21 (s); 2.92 (d); 3.95 (s); 4.22 (m);4.37 (m); 5.90 (m); 6.65 (br); 6.73 (m); 7.37 (m); 7.45 (s) I-193 CH₃ HR3-68 R4-1 NH Y-1 δ = 1.32 (t); 1.95 (s); 2.16 (s); 2.17 (s); 2.32 (s);2.92 (d); 3.97 (s); 4.20 (q); 4.33 (m); 5.90 (m); 6.57 (s); 6.65 (br);7.97 (s) I-194 CH₃ H R3-5 R4-1 O Y-1 δ = 1.95 (s); 3.85 (s); 4.05 (s);4.53 (m); 5.87 (d); 5.93 (m); 7.07 (m); 7.25 (m); 7.55 (m); 7.63 (d)I-195 CH₃ H R3-6 R4-1 O Y-1 δ = 1.95 (s); 3.85 (s); 4.05 (s); 4.55 (m);5.88 (d); 5.93 (m); 7.33 (m); 7.48 (s); 7.53 (d); 7.70 (d) I-196 CH₃ HR3-2 R4-1 O Y-1 δ = 1.95 (s); 3.85 (s); 4.07 (s); 4.55 (m); 5.87 (d);5.92 (m); 6.95 (m); 7.73 (d); 7.80 (m) I-197 CH₃ H R3-4 R4-1 O Y-1 δ =1.95 (s); 2.37 (s); 3.85 (s); 4.07 (s); 4.55 (m); 5.85 (d); 5.92 (m);7.12 (m); 7.28 (m); 7.43 (d); 7.67 (d) I-198 CH₃ H R3-22 R4-1 O Y-1 δ =1.95 (s); 2.35 (s); 3.85 (s); 4.05 (s); 4.57 (m); 5.83 (d); 5.93 (m);7.20 (d); 7.47 (d); 7.66 (d) I-199 CH₃ H R3-24 R4-1 O Y-1 δ = 1.95 (s);3.85 (s); 4.07 (s); 4.60 (m); 5.95 (m); 7.67 (m); 7.77 (d) I-200 CH₃ HR3-22 R4-1 O Y-1 δ = 1.25 (m); 1.95 (s); 2.65 (m); 3.85 (s); 4.05 (s);4.58 (m); 5.83 (d); 5.93 (m); 7.25 (m); 7.48 (m); 7.67 (d I-201 CH₃ HR3-19 R4-1 O Y-1 δ = 1.95 (s); 3.85 (s); 4.07 (s); 4.58 (m); 5.87 (d);5.93 (m); 7.15 (m); 7.30 (m); 7.45 (m); 7.63 (s); 7.70 (d) I-202 CH₃ HR3-7 R4-1 O Y-1 δ = 1.95 (s); 3.85 (s); 4.07 (s); 4.58 (m); 5.90 (d);5.95 (m); 7.45 (m); 7.67 (d); 7.73 (d) I-203 CH₃ H R3-129 R4-1 O Y-1 δ =1.35 (d); 1.95 (s); 3.85 (s); 4.07 (s); 4.55 (m); 5.84 (d); 5.93 (m);6.92 (m); 7.45 (m); 7.60 (d) I-204 CH₃ H R3-11 R4-1 O Y-1 δ = 1.95 (s);2.27 (s); 2.32 (s); 3.85 (s); 4.07 (s); 4.58 (m); 5.85 (d); 5.95 (m);7.15 (d); 7.30 (m); 7.37 (s); 7.66 (d) I-205 CH₃ H R3-3 R4-1 O Y-1 δ =1.95 (s); 2.25 (s); 3.83 (s); 4.05 (s); 4.54 (m); 5.82 (d); 5.92 (m);6.95 (m); 7.25 (m); 7.32 (d) I-206 CH₃ H R3-9 R4-1 O Y-1 δ = 1.93 (s);2.31 (s); 3.85 (s); 4.07 (s); 4.56 (m); 5.85 (m); 5.95 (m); 7.03 (m);7.33 (m); 7.43 (m); 7.64 (m). I-207 CH₃ H R3-18 R4-1 O Y-1 δ = 1.95 (s);3.85 (s); 4.07 (s); 4.58 (m); 5.85 (d); 5.95 (m); 7.05 (m); 7.33 (m);7.55 (m); 7.65 (d) I-208 CH₃ H R3-129 R4-1 NH Y-1 δ = 1.33 (d); 1.95(s); 2.87 (d); 3.97 (s); 4.55 (m); 5.84 (m); 5.95 (m); 6.73 (br); 6.92(d); 7.45 (d); 7.62 (m) I-209 CH₃ H R3-58 R4-1 O Y-1 δ = 1.95 (s); 3.83(s); 4.05 (s); 4.65 (m); 5.95 (m); 7.43 (d); 7.55 (d); 8.23 (s) I-210 ClCH₃ R3-1 R4-1 NH Y-1 δ = 2.10 (s); 2.65 (d); 4.01 (s); 4.95 (s); 5.97(d); 6.85 (br); 7.37 (d);7.50 (d); 7.67 (d) I-211 phenyl ring* R3-1 R4-7Y-1  90° C. R⁶═CH₃ I-212 phenyl ring* R3-98 R4-7 Y-1 151° C. R⁶═CH₃I-213 phenyl ring* R3-130 R4-7 Y-4 R⁶═CH₃ I-214 phenyl ring* R3-131 R4-7Y-4 139-142° C. R⁶═CH₃ I-215 phenyl ring* R3-132 R4-7 Y-4  58-63° C.R⁶═CH₃ I-216 phenyl ring* R3-133 R4-7 Y-1 111-113° C. R⁶═CH₃ I-217phenyl ring* R3-65 R4-7 Y-1  78-88° C. R⁶═CH₃ I-218 phenyl ring* R3-60R4-7 Y-1  83-88° C. R⁶═CH₃ I-219 phenyl ring* R3-67 R4-7 Y-1  87-89° C.R⁶═CH₃ I-220 phenyl ring* R3-62 R4-7 Y-1  82-88° C. R⁶═CH₃ I-221 phenylring* R3-134 R4-7 Y-1  92-98° C. R⁶═CH₃ I-222 phenyl ring* R3-135 R4-7Y-1 141-145° C. R⁶═CH₃ I-223 phenyl ring* R3-64 R4-7 Y-1  88-91° C.R⁶═CH₃ I-224 phenyl ring* R3-59 R4-7 Y-1  82-86° C. R⁶ = CH₃ I-225phenyl ring* R3-63 R4-7 Y-1  64-70° C. R⁶═CH₃ I-226 phenyl ring* R3-136R4-7 Y-1 101-108° C. R⁶═CH₃ I-227 phenyl ring* R3-137 R4-7 Y-1  98-102°C. R⁶═CH₃ I-228 phenyl ring* R3-138 R4-7 Y-1  71-75° C. R⁶═CH₃ I-229phenyl ring* R3-139 R4-7 Y-7  72-74° C. R⁶═CH₃ I-230 phenyl ring* R3-140R4-7 Y-7 δ = 1.65 (s); 3.32 (s); 3.67 (s); R⁶═CH₃ 5.20 (s); 7.07 (m);7.27 (m); 7.47 (m) I-231 phenyl ring* R3-141 R4-7 Y-1 136-138° C. R⁶═CH₃I-232 phenyl ring* R3-142 R4-7 Y-7 δ = 1.65 (s); 3.43 (s); 3.70 (s);R⁶═CH₃ 5.20 (s); 7.30-7.65 (m) I-233 phenyl ring* R3-127 R4-7 Y-1 R_(t)= 3.678 min R⁶═CH₃ I-234 phenyl ring* R3-143 R4-7 Y-1 R_(t) = 4.092 minR⁶═CH₃ I-235 phenyl ring* R3-144 R4-7 Y-1 R_(t) = 4.065 min R⁶═CH₃ I-236phenyl ring* R3-145 R4-7 Y-1 R_(t) = 3.947 min R⁶═CH₃ I-237 phenyl ring*R3-146 R4-7 Y-1 R_(t) = 3.875 min R⁶═CH₃ I-238 phenyl ring* R3-147 R4-7Y-1 R_(t) = 4.100 min R⁶═CH₃ I-239 phenyl ring* R3-68 R4-7 Y-1 R_(t) =3.933 min R⁶═CH₃ I-240 phenyl ring* R3-148 R4-7 Y-4 R_(t) = 3.496 minR⁶═CH₃ I-241 phenyl ring* R3-149 R4-7 Y-4 R_(t) = 4.075 min R⁶═CH₃ I-242phenyl ring* R3-150 R4-7 Y-1 R_(t) = 4.128 min R⁶═CH₃ I-243 phenyl ring*R3-151 R4-7 Y-1 R_(t) = 3.894 min R⁶═CH₃ I-244 phenyl ring* R3-152 R4-7Y-1 R_(t) = 3.875 min R⁶═CH₃ I-245 phenyl ring* R3-153 R4-7 Y-1 R_(t) =3.995 min R⁶═CH₃ I-246 phenyl ring* R3-154 R4-7 Y-1 R_(t) = 4.115 minR⁶═CH₃ I-247 phenyl ring* R3-20 R4-7 Y-1 Rt = 3.715 min R⁶═CH₃ I-248phenyl ring* R3-157 R4-7 Y-1 R_(t) = 3.714 min R⁶═CH₃ I-249 phenyl ring*R3-128 R4-7 Y-1 R_(t) = 3.861 min R⁶═CH₃ I-250 phenyl ring* R3-158 R4-7Y-1 R_(t) = 4.251 min R⁶═CH₃ I-251 phenyl ring* R3-159 R4-7 Y-1 105-107°C. R⁶═CH₃ I-252 phenyl ring* R3-151 R4-7 Y-1 102-104° C. R⁶═Ethyl I-253phenyl ring* R3-1 R4-7 Y-1  96-97° C. R⁶═CHF₂ I-254 phenyl ring* R3-128R4-7 Y-1 Rt = 4.219 min R⁶═Ethyl I-255 phenyl ring* R3-68 R4-7 Y-1 Rt =4.239 min R⁶═Ethyl I-256 phenyl ring* R3-146 R4-7 Y-1 R_(t) = 4.176 minR⁶═Ethyl I-257 phenyl ring* R3-G6 R4-7 Y-1 R_(t) = 4.013 min R⁶═EthylI-258 phenyl ring* R3-160 R4-7 Y-1 δ = 2.15 (s); 3.67 (s); 395 (s);R⁶═CH₃ 5.28 (s); 6.85 (m); 7.45 (m); 7.50 (m); 7.70 (m) I-259 phenylring* R3-161 R4-7 Y-1 δ = 1.33 (t); 2.17 (s); 3.68 (s); R⁶═CH₃ 4.22 (q);5.28 (s); 6.87 (d); 7.45 (m); 7.52 (m); 7.73 (m) I-260 phenyl ring*R3-162 R4-7 Y-1 R_(t) = 3.924 min R⁶═CH₃ I-261 phenyl ring* R3-163 R4-7Y-1 R_(t) = 4.131 min R⁶═CH₃ I-262 phenyl ring* R3-164 R4-7 Y-1 R_(t) =4.141 min R⁶═CH₃ I-263 phenyl ring* R3-165 R4-7 Y-1 R_(t) = 3.916 minR⁶═CH₃ I-264 phenyl ring* R3-166 R4-7 Y-1 R_(t) = 4.220 min R⁶═CH₃ I-265phenyl ring* R3-167 R4-7 Y-1 R_(t) = 4.050 min R⁶═CH₃ I-266 phenyl ring*R3-149 R4-7 Y-8 δ = 2.03 (s); 3.71 (s); 7.45-7.62 (m) R⁶═CH₃ I-267phenyl ring* R3-168 R4-7 Y-1 δ = 2.20 (s); 2.40 (s); 3.69 (s); R⁶═CH₃5.20 (s); 6.70 (s); 7.12 (s); 7.42 (s); 7.53 (m); 7.72 (m); 7.91 (s)I-268 phenyl ring* R3-169 R4-7 Y-1 δ = 2.11 (s); 2.18 (s); 3.62 (s);R⁶═CH₃ 3.72 (s); 5.21 (s); 6.77 (s); 6.96 (s); 7.25 (s); 7.53 (m); 7.72(m); 8.91 (s) I-269 phenyl ring* R3-170 R4-7 Y-1 δ = 2.00 (s); 2.05 (s);2.16 (s); R⁶═CH₃ 2.21 (s); 3.70 (s); 5.16 (s); 6.72 (s); 6.82 (s); 7.50(m); 7.74 (m) I-270 phenyl ring* R3-171 R4-7 Y-1 δ = 2.16 (s); 2.39 (s);2.53 (s): R⁶═CH₃ 3.70 (s); 5.19 (s); 6.70 (s); 7.53 (m); 7.72 (m) I-271phenyl ring* R3-172 R4-7 Y-1 δ = 2.18 (s); 2.29 (s); 3.70 (s); R⁶═CH₃5.18 (s); 6.71 (s); 7.06 (s); 7.50 (m); 7.71 (m); 8.38 (s); 8.44 (s)I-272 phenyl ring* R3-173 R4-7 Y-1 δ = 1.28 (m); 2.12 (s); 3.00 R⁶═CH₃(broad); 3.58 (m); 3.69 (s); 5.52 (s); 6.28 (s); 7.45 (m); 7.72 (m)I-273 phenyl ring* R3-174 R4-7 Y-1 δ = 0.97 (m); 1.02 (m); 1.20 (m);R⁶═CH₃ 1.90 (m); 2.05 (s); 2.62 (m); 3.68 (s); 5.51 (s); 5.84 (s);7.50(m); 7.73 (m) I-274 phenyl ring* R3-175 R4-7 Y-8 R_(t) = 3.715 minR⁶═CH₃ I-275 CH₃ H R3-20 R4-1 O Y-1 δ = 1.95 (s); 3.85 (s); 4.07 (s);4.58 (m); 5.92 (m); 7.45 (m); 7.52 (m); 7.75 (m); 7.84 (d) I-276 CH₃ HR3-12 R4-1 O Y-1  72-74° C. I-277 CH₃ H R3-15 R4-1 O Y-1  73-75° C.I-278 CH₃ H R3-176 R4-1 O Y-1 δ = 1.97 (s); 3.85 (s); 4.07 (s); 4.58(d); 5.90 (d); 5.95 (m); 7.17 (t); 7.43 (m); 7.65 (m) I-279 CH₃ H R3-98R4-1 O Y-1  90-92° C. I-280 CH₃ H R3-20 R4-1 NH Y-1 101-103° C. I-281CH₃ H R3-12 R4-1 NH Y-1 112-115° C. I-282 CH₃ H R3-15 R4-1 NH Y-1 93-95° C. I-283 CH₃ H R3-176 R4-1 NH Y-1  84-86° C. I-284 CH₃ H R3-98R4-1 NH Y-1 δ = 1.95 (s); 2.27 (s); 2.93 (d); 3.97 (s); 4.48 (m); 5.93(m); 6.42 (m); 6.67 (broad); 6.80 (d); 7.37 (d); 7.45 (m); 7.68 (m);7.83 (m) I-285 CH₃ H R3-1 R4-4, O Y-1 δ = 1.93 (s); 3.72 (s); 3.81 (s);R⁵═OCH₃ 4.78 (d); 5.73 (t); 5.90 (d); 7.36 (d); 7.55 (d); 7.70 (d) I-286CH₃ H R3-51 R4-1 O Y-1 δ = 1.93 (s); 2.45 (s); 3.82 (s); 4.05 (s); 4.60(d); 5.92 (t); 7.25- 7.50 (m) I-287 C₂H₅ H R3-1 R4-1 NH Y-1 δ = 1.05(t); 2.30 (q); 2.90 (d); 3.97 (s); 4.58 (m); 5.93 (m); 6.70 (broad);7.35 (m); 7.53 (m); 7.68 (s) I-288 CH₃ H R3-58 R4-1 NH Y-1 δ = 1.95 (s);2.90 (d); 3.97 (s); 4.63 (m); 5.95 (m); 6.75 (broad); 7.43 (m); 7.55(m); 8.23 (s) I-289 CH₃ H R3-51 R4-1 NH Y-1 δ = 1.93 (s); 2.45 (s); 2.83(d); 3.95 (s); 4.58 (m); 5.92 (m); 6.73 (broad); 7.30-7.50 (m) I-290 CH₃H R3-1 R4-4, O Y-1 δ = 1.18 (m); 1.95 (s); 3.45 R⁵═C₂H₅ (broad); 3.73(s); 4.67 (m); 5.70 (m); 5.90 (m); 7.35 (m); 7.53 (m); 7.67 (m) I-291CH₃ H R3-39 R4-1 O Y-1  72° C. I-292 CH₃ H R3-44 R4-1 O Y-1 106-110° C.I-293 CH₃ H R3-44 R4-1 NH Y-1 177° C. I-294 CH₃ H R3-177 R4-1 O Y-1 δ =1.93 (s); 3.20 (m); 3.28 (m); 3.83 (s); 3.90 (m); 4.05 (s); 4.42 (m);4.50 (m); 5.88 (m); 5.94 (s); 6.83 (m); 7.25 (m); 7.50 (s) I-295 CH₃ HR3-39 R4-1 NH Y-1 142° C. I-296 Iso-butyl H R3-1 R4-1 O Y-1 δ = 0.93(m); 1.60 (m); 2.15 (d); 3.84 (s); 4.07 (s); 4.62 (m); 5.89 (m); 7.35(d); 7.53 (d); 7.67 (s) I-297 CH₃ H R3-29 R4-1 O Y-1 δ = 1.95 (s); 3.85(s); 4.07 (s); 4.65 (m); 5.95 (m); 7.27 (m); 7.87 (m); 8.35 (s) I-298CH₃ H R3-36 R4-1 O Y-1 δ = 1.95 (s); 3.85 (s); 4.07 (s); 4.65 (m); 5.95(m); 7.63 (m); 7.67 (m); 7.93 (s); 8.37 (s) I-299 Iso-butyl H R3-1 R4-1NH Y-1 177° C. I-300 C₂H₅ H R3-58 R4-1 O Y-1  87° C. I-301 CH₃ H R3-29R4-1 NH Y-1 140° C. I-302 CH₃ H R3-36 R4-1 NH Y-1 125° C. I-303 CH₃ HR3-33 R4-1 O Y-1 δ = 1.95 (s); 3.83 (s); 4.05 (s); 4.65 (m); 5.95 (m);7.37 (m); 7.57 (m); 8.27 (s) I-304 CH₃ H R3-54 R4-1 O Y-1 δ = 1.25 (m);1.95 (s); 2.68 (m); 3.83 (s); 4.05 (s); 4.65 (m); 5.95 (m); 7.30 (m);7.51 (m); 8.20 (s) I-305 CH₃ H R3-33 R4-1 NH Y-1 126° C. I-306 CH₃ HR3-54 R4-1 NH Y-1 128° C. I-307 CH₃ H R3-178 R4-1 O Y-1 δ = 1.95 (s);2.27 (s); 3.82 (s); 4.07 (s); 4.62 (m); 5.95 (m); 7.28 (m); 7.36 (m);7.93 (s) I-308 CH₃ H R3-130 R4-1 O Y-4 δ = 1.95 (s); 2.25 (s); 3.80 (s);4.05 (s); 4.55 (m); 5.90 (m); 7.25- 7.60 (m); 7.77 (m); 7.85 (s); 8.05(s); 8.27 (s) I-309 CH₃ H R3-130 R4-1 NH —CH═N—O—CH₂— δ = 1.95 (s); 2.88(d); 3.96 (s); 4.50 (m); 5.92 (m); 6.70 (broad); 7.25-7.60 (m); 7.76(m); 8.05 (s); 8.08 (s); 8.27 (s) I-310 CH₃ H R3-42 R4-1 O Y-1 116° C.I-311 C₂H₅ H R3-58 R4-1 NH Y-1 154° C. I-312 CH₃ H R3-30 R4-1 NH Y-1167° C. I-313 CH₃ H R3-178 R4-1 NH Y-1 143° C. I-314 CH₃ H R3-42 R4-1 NHY-1 147° C. I-315 CH₃ H R3-40 R4-1 NH Y-1 153° C. I-316 CH₃ H R3-177R4-1 NH Y-1 δ = 1.93 (s); 2.88 (d); 3.20 (m); 3.28 (m); 3.90 (m); 3.95(s); 4.42 (m); 4.50 (m); 5.90 (m); 5.95 (s); 6.67 (broad); 6.86 (m);7.25 (m); 7.50 (s) I-317 CH₃ H R3-179 R4-1 NH Y-1 δ = 1.83 (s); 1.93(s); 2.18 (s); 2.42 (m); 2.70 (m); 2.88 (d); 3.83 (s); 3.95 (s); 4.35(m); 5.90 (m); 6.65 (m); 6.93 (m) I-318 CH₃ H R3-38 R4-1 O Y-1  87° C.I-319 CH₃ H R3-32 R4-1 O Y-1 δ = 1.93 (s); 2.27 (s); 3.80 (s); 4.05 (s);4.62 (m); 5.95 (m); 7.30 (m); 7.93 (s) I-320 CH₃ H R3-34 R4-1 NH Y-1120° C. I-321 CH₃ H R3-38 R4-1 NH Y-1 143° C. I-322 CH₃ H R3-37 R4-1 NHY-1 117° C. I-323 CH₃ H R3-40 R4-1 O Y-1 118° C. I-324 CH₃ H R3-37 R4-1O Y-1 δ = 1.93 (8); 2.23 (s); 2.35 (s); 3.80 (s); 4.05 (s); 4.62 (m);5.95 (m); 7.15 (m); 7.91 (s) I-325 CH₃ H R3-43 R4-1 NH Y-1 136° C. I-326CH₃ H R3-34 R4-1 O Y-1 δ = 1.95 (s); 3.83 (s); 4.05 (s); 4.63 (m); 5.95(m); 7.67 (m); 7.82 (m); 8.42 (s) I-327 CH₃ H R3-32 R4-1 NH Y-1 δ = 2.07(s); 2.42 (s); 2.92 (d); 4.08 (s); 4.78 (m); 6.08 (m); 6.93 (broad);7.45 (m); 8.08 (s) I-328 CH₃ H R3-41 R4-1 NH Y-1 δ = 1.95 (s); 2.90 (d);3.95 (s); 4.65 (m); 5.93 (m); 6.73 (broad); 7.30 (m); 7.55 (m); 8.23 (s)I-329 CH₃ H R3-28 R4-1 NH Y-1  94° C. I-330 CH₃ H R3-50 R4-1 NH Y-1 130°C. I-331 CH₃ H R3-41 R4-1 O Y-1 δ = 1.95 (s); 3.87 (s); 4.06 (s); 4.63(m); 5.93 (m); 7.32 (m); 7.55 (m); 8.23 (s) I-332 C₂H₅ H R3-2 R4-1 O Y-1δ = 1.05 (t); 2.30 (m); 3.82 (s); 4.05 (s); 4.62 (d); 5.90 (m); 6.93(m); 7.73 (m); 7.80 (m) I-333 CH₃ H R3-180 R4-1 O Y-1 δ = 1.95 (s); 2.27(s); 3.85 (s); 4.07 (s); 4.40 (m); 5.88 (m); 6.66 (d); 6.78 (m); 7.37(m); 7.45 (m); 7.83 (d) I-334 CH₃ H R3-77 R4-1 O Y-1 123-124° C. I-335CH₃ H R3-119 R4-1 O Y-4 δ = 1.90 (s); 2.12 (s); 3.83 (s); 3.92 (s); 4.03(s); 4.33 (m); 5.74 (m); 7.18-7.45 (m) I-336 CH₃ H R3-80 R4-1 O Y-1133-134° C. I-337 CH₃ H R3-180 R4-1 NH Y-1 δ = 1.95 (s); 2.27 (s); 2.90(d); 3.97 (s); 4.40 (m); 5.88 (m); 6.66 (broad); 6.82 (m); 7.37 (m);7.45 (m); 7.81 (d) I-338 CH₃ H R3-79 R4-1 O Y-1  94-97° C. I-339 CH₃ HR3-119 R4-1 NH Y-4 δ = 1.90 (s); 2.12 (s); 2.85 (d); 3.92 (s); 4.33 (m);5.75 (m); 6.60 (broad); 7.18-7.45 (m) I-340 CH₃ H R3-130 R4-1 O—CH═N—O—CH₂— δ = 1.95 (s); 3.82 (s); 4.05 (s); 4.52 (m); 5.87 (m);7.25-7.60 (m); 7.75 (m); 7.80 (s); 8.05 (s); 8.26 (s) I-341 CH₃ H R3-130R4-1 NH Y-4 δ = 1.95 (s); 2.25 (s); 2.83 (d); 3.97 (s); 4.54 (m); 5.93(m); 6.75 (broad); 7.25-7.60 (m); 7.77 (m); 7.82 (s); 8.02 (s); 8.29 (s)I-342 CH₃ H R3-181 R4-1 NH Y-1 δ = 1.95 (s); 2.27 (s); 2.88 (d); 3.97(s); 4.39 (m); 5.93 (m); 6.67 (broad); 6.80 (m); 7.08 (m); 7.27 (m);7.45 (m) I-343 CH₃ H R3-182 R4-1 NH Y-1 δ = 1.95 (s); 2.27 (s); 2.91(d); 3.98 (s); 4.41 (m); 5.93 (m); 6.70 (broad); 6.85 (m); 7.37 (m);7.65 (m) I-344 CH₃ H R3-183 R4-1 NH Y-1 δ = 1.95 (s); 2.25 (s); 2.91(d); 3.98 (s); 4.40 (m); 5.93 (m); 6.66 (broad); 6.83 (m); 7.25-7.46 (m)I-345 CH₃ H R3-184 R4-1 NH Y-1 δ = 1.95 (s); 2.25 (s); 2.90 (d); 3.85(s); 3.98 (s); 4.38 (m); 5.93 (m); 6.66 (broad); 6.82 (m); 7.30 (m)I-346 CH₃ H R3-185 R4-1 NH Y-1 δ = 1.95 (s); 2.20 (s); 2.88 (d); 3.95(s); 4.30 (m); 4.98 (s); 5.92 (m); 6.65 (m); 6.80 (m); 7.40 (m) I-347CH₃ H R3-69 R4-1 NH Y-1 δ = 1.95 (s); 2.90 (d); 3.95 (s); 4.65 (m); 5.92(m); 6.67 (broad); 6.87 (m); 7.25 (m); 7.67 (m) I-348 CH₃ H R3-186 R4-1NH Y-1 δ = 1.42 (m); 1.95 (s); 2.27 (s); 2.91 (d); 2.96 (m); 3.98 (s);4.42 (m); 5.93 (m); 6.70 (broad); 6.83 (m); 7.87 (m) I-349 C₂H₅ H R3-5R4-1 NH Y-1 98° C. I-350 CH₃ H R3-88 R4-1 O Y-1 δ = 1.95 (s); 3.53 (s);3.85 (s); 4.05 (s); 4.50 (m); 5.65 (s); 5.90 (m); 7.28 (m); 7.50 (s)I-351 CH₃ H R3-88 R4-1 NH Y-1 δ = 1.95 (s); 2.90 (d); 3.50 (s); 3.97(s); 4.48 (m); 5.65 (m); 5.93 (m); 6.70 (broad); 7.28 (m); 7.50 (s)I-352 CH₃ H R3-76 R4-1 NH Y-1 δ = 1.95 (s); 2.27 (s); 2.87 (d); 3.95(s); 4.63 (m); 5.93 (m); 6.66 (broad); 7.35 (m); 7.77 (m) I-353 CH₃ HR3-187 R4-1 NH Y-1 δ = 1.95 (s); 2.87 (d); 3.97 (s); 4.63 (m); 5.90 (d);5.95 (m); 6.70 (broad); 7.48 (m); 7.85 (m); 7.97 (d) I-354 CH₃ H R3-188R4-1 NH Y-1 δ = 1.93 (s); 2.77 (d); 3.93 (s); 4.54 (m); 5.92 (m); 6.80(broad); 7.33 (m); 7.45 (m) I-355 CH₃ H R3-189 R4-1 NH Y-1 δ = 1.95 (s);2.85 (d); 3.95 (s); 4.55 (m); 5.92 (m); 6.70 (broad); 7.23 (m); 7.40(m); 7.64 (s); 7.78 (d) I-356 CH₃ H R3-193 R4-1 NH Y-1 δ = 1.94 (s);2.87 (d); 3.94 (s); 4.44 (m); 5.17 (s); 5.67 (d); 5.88 (m); 6.70(broad); 6.86 (m); 7.20 (m); 7.37 (d) I-357 CH₃ H R3-194 R4-1 NH Y-1 δ =1.95 (s); 2.80 (d); 3.95 (s); 4.55 (m); 5.87 (d); 5.93 (m); 6.75(broad); 7.25 (m); 7.35 (m); 7.45 (m); 7.55 (m); 7.70 (d) I-358 CH₃ HR3-83 R4-1 NH Y-1 δ = 1.95 (s); 2.90 (d); 3.95 (s); 4.57 (m); 5.92 (m);6.13 (s); 6.83 (broad); 7.45 (m); 7.35 (m); 7.70 (m) I-359 CH₃ H R3-195R4-1 NH Y-1 δ = 1.95 (s);2.50 (s); 2.88 (d); 3.95 (s); 4.57 (m); 5.85(d); 5.95 (m); 6.70 (broad); 6.90 (m); 7.60 (m); 8.33 (d) *phenyl ringdenotes that R¹ and R² together with the two carbon atoms linking themform a phenyl ring. Isobutyl = 2-methyl-1-propyl. m.p. = melting point;R_(t) = HPLC Retention time. HPLC-data: RP-18 column (Chromolith SpeedROD 50 × 4.6 mm from Merck KgaA, Germany), 1.8 ml/min, injection volume2 μl, column temperature 40° C. Eluent: Acetonitrile + 0.1%trifluoroacetic acid (TFA)/water + 0.1% TFA (gradient %: 95 to 95:5within 5 min), 40° C. MS: Quadrupole electrospray ionisation, 80 V (pos.mode).

II. EXAMPLES OF THE ACTION AGAINST HARMFUL FUNGI

The fungicidal action of the compounds of the formula I was demonstratedby the following experiments:

II.1 Microtiter Tests

The active substances were formulated separately as a stock solution indimethyl sulfoxide (DMSO) at a concentration of 10 000 ppm.

Use Example 1

Activity against the Septoria blotch pathogen caused by Septoria triticiin the microtiter test

Fungal strains used:

-   -   a) Septoria tritici (Qo-inhibitor sensitive, wild-type)    -   b) Septoria tritici (Qo-inhibitor-resistant, G143A mutant)

100 ml 2% Malt extract in water at pH6.8 were inoculated withmicrospores from 2 week old cultures grown on 2% malt extract+2% agar inPetri dishes and incubated for 3 days on a rotary shaker at 24° C. und150 rpm. The culture was harvested, glycerol was added (15% (v/v) andkept frozen at −20° C. in aliquots of 1 ml.

1 ml stock suspension was thawed and suspended into 800 ml of 2% maltextract in water at pH 6.8. Compounds were diluted from stock solutionin (dimethylsulfoxide) DMSO in 10 steps. The compound solutions werediluted 1/5 with sterile deionized water before use. 5 μl of thecompound solutions were transferred into empty microplates. The plateswere then filled with 195 μl of the microspore suspension of eachstrain.

The antifungal activity was determined by measuring the turbidity of aculture in 96-well microplates in the presence of test compounds. Fungalgrowth was measured by recording the optical density at 620 nm every 15h for 150 h. The relative antifungal activity was calculated bycomparison of the effect of the test compounds with the effect of a DMSOcontrol and a standard fungicide.

IC₅₀-values (concentration of test compound resulting in 50% inhibitionof fungal growth) were calculated from the resulting dose-response foreach compound and strain. The initial concentration of the testcompounds and the 10 steps of dilution (1:4 each) allowed IC₅₀-valuesfrom 0.001 to 100 μmol/l (μM) to be assessed.

TABLE II Resistant Sensitive Septoria tritici Septoria triticiResistance isolate isolate factor (G143A mutation) (wild type) RF =R-IC₅₀/ Compound (R-IC₅₀) [μM] (S-IC₅₀) [μM] S-IC₅₀ Azoxystrobin >1003.5 n.d. Dimoxystrobin >100 7.1 n.d. Enestroburin >100 4.5 n.d.Kresoximmethyl >100 0.76 n.d. Metominostrobin >100 >100 n.d.Orysastrobin >100 27 n.d. Picoxystrobin >100 2.3 n.d.Pyrametostrobin >100 >100 n.d. Pyraoxystrobin >100 1.6 n.d.Pyraclostrobin 3.4 0.0012 2882 Trifloxystrobin >100 0.52 n.d. I-5  2.20.083 26 I-6  8.3 0.34 24 I-82  6.8 1.1 6 I-83  7.6 1.6 4.6 I-84  16.10.5 33 I-85  22 0.8 29 I-90  26 1.0 26 I-91  27 1.6 17 I-94  12 0.6 22I-95  29 2.2 14 I-97  49 1.7 29 I-191 37 1.3 29 I-211 1.1 0.44 2.6 I-2128.3 1.4 6 I-213 0.057 0.076 0.7 I-215 48 1.7 28 I-216 12.0 6.3 2.0 I-21763 6.3 10 I-218 79 5.6 14 I-221 10 3.4 3 I-223 19 2.7 7 I-224 5.4 1.73.2 I-225 72 3.4 21 I-228 10 3.4 3.0 I-230 25 3.2 8 I-233 2.7 0.24 12I-234 4 2.4 1.7 I-235 51 13 4 I-236 24 6 4 I-238 12 6 1.9 I-243 15 4.13.6 I-244 1.3 0.6 2.0 I-247 9 5 1.9 I-249 11 2.4 5 I-250 97 19 5 I-25542 19 2.2 I-256 24 21 1.1 I-257 67 15 4.5 I-260 3.3 2.3 1.4 I-261 5 2.91.6 I-262 1.6 1 1.6 I-265 4 3.8 1.1 I-267 5 2.9 1.7 I-269 74 8 10 I-27057 6 10 I-271 7 1.9 3.9 I-273 22 5 4 I-274 19 9 2.0 I-287 18 1.5 12I-288 28 3.5 8.0 I-291 18 1.0 18.0 I-292 33 7.9 4.2 I-298 31 3.6 8.6I-303 4.6 0.27 17.0 I-304 9.1 0.53 17.2 I-305 32 9.3 3.4 I-307 67 19.03.5 I-310 11 0.39 28.2 I-319 102 17.0 6.0 I-324 38 1.9 20.0 I-326 18 1.215.0 I-331 25 1.8 13.9 I-339 21 1.0 21.0

While commercial strobilurine type fungicides are do not show anyactivity against the resistant Septoria strain, containing a mutation inthe mitochondrial cytochrome b gene conferring resistance to Qoinhibitors (G143A) while being active against sensitive wild typestrains, compounds I have been active against both, the resistant andthe wild-type strains. In general, the resistance factor ratio (RF)calculated from the IC50 values determined for both Septoria strains,was below 30 for the compounds I according to the invention. However,resistance factor ratios for commercial strobilurine type compounds arein most cases greater than 100 and usually greater than several hundreds(for details see e.g. FRAC, Mutations associated with Qol-resistance,December 2006; http://frac.info/frac/work/Mutations %20associated%20with %20Qol%20resistance.pdf and citations cited therein).

II.2 Comparative Examples A) Field Trials

Compounds used:

Compound I-6 was used as 50 g/l EC formulation. Pyraclostrobin was usedas commercial product HEADLINE.

Compounds used:

Trial 1: Efficacy Against Septoria tritici on Winter Wheat

The trial was conducted under field conditions in Böhl-Iggelheim,Rhineland-palatinate, Germany. Seeds of winter wheat (cv. Riband) wereplanted and grown under standard conditions with adequate supply ofwater and nutrients. At growing stage GS 32 (Apr. 14, 2011), a firstcompound treatment (200 g a.i. per ha) was made with a water volume of400 L/ha, which was repeated 21 days later at growing stage GS 39. Nofurther fungicide treatments were applied. Infection with fungalpathogens (e.g. Septoria tritici) occurred naturally. The evaluation ofthe disease incidences for Septoria tritici 20, 33 and 46 days after thelast treatment (DAA) are shown in table Ill. In the last row, theevaluation of the percentage of Qo inhibitor-resistant Septoria triticiisolates with the G143A mutation after the treatments is given.

TABLE III Percentage of G143A mutation Disease (%) (%) in Concentration20 33 46 Septoria tritici Treatment (g a.i./ha) DAA DAA DAA isolatesCompound 200  1  6 36 100 I-6 Pyraclostrobin 200  8 32 93 100 untreated— 13 47 96  65

In this test, the fungal pathogen Septoria tritici has been completelyselected towards Qo inhibitor-resistant isolates by each of thetreatments with the strobilurin-analogue compounds Pyraclostrobin andcompound I-6. Due to this high resistance level, Pyraclostrobin showedinsufficient control level although it has been used at commercial doselevels, whereas compound I-6 was capable to control the Qoinhibitor-resistant isolates of Septoria tritici with the G143 mutation.

Trial 2: Efficacy Against Septoria tritici on Winter Wheat

This trial was conducted under field conditions in Limburgerhof,Rhineland-Palatinate, Germany. Seeds of winter wheat (cv. Riband) wereplanted and grown under standard conditions with adequate supply ofwater and nutrients. At growing stage GS 33 (Apr. 8, 2011), a firstcompound treatment (200 g a.i per ha) was made with a water volume of400 L/ha, which was repeated 26 days later at growing stage GS 39. Nofurther fungicide treatments were applied. Infection with fungalpathogens (e.g. Septoria tritici) occurred naturally. The evaluation ofthe disease incidences for Septoria tritici 19 and 34 days after thelast treatment (DAA) are shown in Table IV. In the last row, theevaluation of the percentage of Qo inhibitor-resistant Septoria triticiisolates with the G143A mutation after the treatments is given.

TABLE IV Percentage of G143A mutation (%) in Septoria ConcentrationDisease (%) tritici Treatment (g a.i./ha) 19 DAA 34 DAA isolatesCompound I-6 200  3 12  99 Pyraclostrobin 200  5 28 100 untreated — 1036  94

In this test, about the entire population of the fungal pathogenSeptoria tritici has been Qo inhibitor-resistant (as evaluated at theend of the trial). Due to this high resistance level, Pyraclostrobin hasshown antifungal activity only slightly above the untreated controlalthough it has been used at commercial dose levels. However compoundI-6 was capable to reduce the infection by Qo inhibitor-resistantSeptoria tritici with the G143 mutation significantly.

B) Glass House Trials

The spray solutions were prepared in several steps:

The stock solution was prepared as follows: 1.26 ml of a 1:1 mixture ofcyclohexanone and dimethylsulfoxide was added to 8.4 mg of activeingredient. Next, 40.74 ml of a mixture of water, acetone (10%), theemulsifier Wettol (0.1%) and the wetting agent Silwet (0.05%) was added.This stock solution was then further diluted with the describedsolvent-emulsifier-water mixture to the desired concentrations.

Trial 3: Control of Leaf Blotch on Wheat Caused by Caused by TwoSeptoria tritici Isolates Containing the G143A in the Cytochrome b Genefor their Cytochrome Bc₁ Complex

Wheat plants were grown in pots. These plants were sprayed to run-offwith an aqueous suspension, containing the desired concentration ofactive ingredient. The next day, the treated plants were inoculated withan aqueous suspension of Septoria tritici. After inoculation, the trialplants were covered with a lid and immediately transferred to a chamberwith a relative humidity of about 83 to 85% and 19.5 to 20° C. After 4days the lid was removed. Altogether, the trial plants were cultivatedfor about 28 days in that greenhouse chamber. The extent of fungalattack on the leaves was then visually assessed as % diseased leaf area.

TABLE VII Resistant Septoria Resistant Septoria tritici isolate 1tritici isolate 2 Conc. (G143A mutation) (G143A mutation) Treatment(ppm) Disease level (%) Disease level (%) I-7  200 3 0 I-7  100 3 1 I-7 50 20 5 I-7  25 80 15 I-7  12.5 100 90 I-211 200 1 0 I-211 100 3 1 I-21150 10 5 I-211 25 60 10 I-211 12.5 80 30 I-14  200 3 1 I-14  100 15 5I-14  50 70 15 I-14  25 80 70 I-14  12.5 100 90 I-6  200 1 0 I-6  100 33 I-6  50 3 3 I-6  25 10 15 I-6  12.5 50 20 I-11  200 1 1 I-11  100 3 5I-11  50 30 30 I-11  25 90 50 I-11  12.5 100 70 Pyraclostrobin 200 30 15Pyraclostrobin 100 90 25 Pyraclostrobin 50 100 40 Pyraclostrobin 25 10060 Pyraclostrobin 12.5 100 60 Trifloxystrobin 200 90 60 Trifloxystrobin100 90 70 Trifloxystrobin 50 90 70 Trifloxystrobin 25 100 70Trifloxystrobin 12.5 100 80

III. MOLECULAR MODELING III.1 Structural Models of Wild-Type and G143AMutant Binding Site

Structural models of the binding site of wild-type and G143A cytochromebc₁ complex were generated based on the crystallographic structure ofbovine cytochrome bc₁ complex with azoxystrobin bound to the Qo-site(PDB: 1SQB: Esser et al. J Mol Biol 341, 281-302 (2004)).

The structure was imported into Schrödinger Maestro (version 9.0,Schrödinger, LLC, New York, N.Y., 2009).

Cytochrome b was isolated from the structure of the complex and treatedwith the Schrödinger Protein Preparation Wizard (Schrödinger Suite 2009Protein Preparation Wizard; Epik version 2.0, Schrödinger, LLC, NewYork, N.Y., 2009; Impact version 5.5, Schrödinger, LLC, New York, N.Y.,2009, Prime version 2.1, Schrödinger, LLC, New York, N.Y., 2009).

This structure was used as the model for the wild-type binding sitewithout further changes.

The model of the G143A mutant was generated by changing a hydrogen inGlycine 143 of the wild-type model into a methyl group, therebygenerating S-Alanine, using Schrödinger Maestro. Amino acids in a sphereof 5 Á around the co-crystallized molecule of azoxystrobin wereenergy-minimized using Schrödinger MacroModel (version 9.7, Schrödinger,LLC, New York, N.Y., 2009).

III.2 Molecular Docking

Structures of inhibitors were prepared for docking with SchrödingerLigPrep (version 2.3, Schrödinger, LLC, New York, N.Y., 2009) and dockedinto the structural models using Schrödinger Glide (version 5.5,Schrödinger, LLC, New York, N.Y., 2009).

III.3 Graphics of Inhibitors Bound to Cytochrome Bc₁ Complex

Graphical representations of poses from the docking runs were generatedusing Molecular Operating Environment (MOE; 2010.10; Chemical ComputingGroup Inc., 1010 Sherbooke St. West, Suite #910, Montreal, QC, Canada,H3A 2R7, 2010) and refined using the GNU Image Manipulation Program(GIMP, version 2.6.8, 2008).

As illustrated in FIG. 1 molecular modelling of an artificial Qoinhibitor-resistant cytochrome bc₁ complex with the mutation G143A (seebelow for details) has been carried out. Docking of the commercialstorbilurine analogue compound pyraclostrobin shows the steric clashresulting in impaired binding of this active ingredient in the G143Amutant cytochrome bc₁ complex. The compounds of the present inventionlargely avoid this steric clash by either replacing the central phenylring of pyraclostrobin with a smaller and/or more flexible two carbonunit which may be suitably substituted or by replacing the well knownpharmacophores with the smaller tetrazolinone moiety R4-7.

III.4 Number of Van-Der-Waals Clashes Between Inhibitors and AlanineG143A

The docked ligands were transferred to the G143A binding site modelkeeping the coordinates from docking into the wild-type model. Thereby,complexes between the G143A binding site and ligands were formed. Thosewere used as starting structures for the following energy minimizationusing Schrödinger MacroModel. During these simulations, only the ligandwas allowed to move freely, the protein was considered “frozen”. Theposes generated by this procedure were considered as the relaxed stateof the inhibitors after introduction of the G143A mutation.

Two atoms are considered to be sterically clashing, if the distancebetween their centers is shorter than 0.9 times the sum of theirVan-der-Waals radii. For the atoms pairs relevant for strobilurininteraction with Alanine 143 the respective distances are described inTable V.

TABLE V Clash Atom 1 vdW-Radius 1 Atom 2 vdW-Radius 2 vdW-Sum Distance C1.70 C 1.70 3.40 3.06 C 1.70 N 1.55 3.25 2.93 C 1.70 O 1.52 3.22 2.90 C1.70 H 1.20 2.90 2.61 H 1.20 N 1.55 2.75 2.48 H 1.20 O 1.52 2.72 2.45

After minimization in the G143A binding site as described above, thenumber of steric Van-der-Waals clashes with Alanine 143 was counted foreach inhibitor. The results are given in the Table VI.

TABLE VI Compound No. of clashes I-5 3 I-6 3 Pyrametostrobin 6Metominostrobin 6 Azoxystrobin 7 Enestroburin 7 Pyraclostrobin 7Dimoxystrobin 7 Orysastrobin 7 Pyraoxystrobin 8 Picoxystrobin 8Trifloxystrobin 8 Kresoxim-Methyl 8

It was found that compounds I have a small number of stericVan-der-Waals clashes and also have unexpectedly high activity againstQo inhibitor-resistant fungal strains harboring said G143A mutation inmicrotiter titer tests as well as in field trials on sites which have ahigh portion of Qo inhibitor-resistant fungi strains harboring saidG143A mutation (see below).

The invention claimed is:
 1. A method for combating phytopathogenicfungi containing a mutation in the mitochondrial cytochrome b geneconferring resistance to Qo inhibitors, wherein the mutations is G143A,comprising applying agrochemical composition wherein said compositioncomprises an auxiliary and a pesticidally effective amount of at leastone compound of formula (I)

wherein: R¹ and R² together with the two carbon atoms linking them forma phenyl ring and R⁴ is 4-methyl-1,4-dihydro-tetrazol-5-one-1-yl, andwherein the abovementioned phenyl ring may carry 1, 2, 3 or up to themaximum number of identical or different groups R^(a) whichindependently of one another are selected from: R^(a) halogen, CN,nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl and C₁-C₄-haloalkoxy;Y is a direct bond or a divalent group selected from —OCH₂—, —CH₂—,—CH₂CH₂—, —C(Z)═N—O—CH₂—, —CHZ—C(Z)═N—O—CH₂—, —O—N═C(Z)—C(Z)═N—O—CH₂—,—C(═O)—C(Z)═N—O—CH₂— and —C(═N—O—Z)—C(Z)═N—O—CH₂—, where the bonddepicted on the left side of the divalent group Y is attached to R³, andthe bond depicted on the right side is attached to the carbon atom beingsubstituted by R², and Z, which may be the same or different to anyother Z, is hydrogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl; R³ is

wherein # indicates the point of attachment to the linker moiety Y;wherein the phenyl may carry 1, 2, 3 or up to the maximum possiblenumber of identical or different groups R^(c), which may be the same ordifferent to any other R^(c), is halogen; or an N-oxide or anagriculturally acceptable salt thereof.
 2. The method of claim 1,wherein in formula (I) Y is —OCH₂, —CH₂CH₂—, —C(CH₃)═N—O—CH₂—,—O—N═C(CH₃)—C(CH₃)═N—O—CH₂— or —C(═N—O—CH₃)—C(CH₃)═N—O—CH₂—.
 3. Themethod of claim 1, wherein the phytopathogenic fungi are selected fromthe group consisting of Alternaria alternata, Blumeria graminis,Pyricularia oryzae, Septoria tritici, Mycosphaerella fijiensis, Venturiainaequalis, Pyrenophora teres, Pyrenophora tritici-repentis andPlasmopara viticola.
 4. The method of claim 3, wherein thephytopathogenic fungus is Septoria tritici.
 5. The method of claim 1,comprising: treating the phytopathogenic fungi or the materials, plants,the soil or seeds that are at risk of being diseased fromphytopathogenic fungi with an effective amount of a compositioncomprising at least one compound of formula I.
 6. The method of claim 5,comprising: a) identifying the phytopathogenic fungi, or the materials,plants, the soil or seeds that are at risk of being diseased fromphytopathogenic fungi, and b) treating said fungi or the materials,plants, the soil or seeds with an effective amount of a compositioncomprising at least one compound of formula I.